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UBC Theses and Dissertations

Reactions of some unsaturated fluorocarbon derivatives with organo compounds of arsenic, silicon, germanium… Stylan, Garrick Ernest 1965

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The University of B r i t i s h Columbia FACULTY OF GRADUATE STUDIES PROGRAMME OF THE FINAL ORAL EXAMINATION FOR THE DEGREE OF DOCTOR OF PHILOSOPHY of GARRICK ERNEST STYAN. B.Sc, (Hon.), The University of B r i t i s h Columbia 1964 WEDNESDAY, JUNE 23rd, 1965, AT 10:30 A.M. IN ROOM 261, CHEMISTRY BUILDING COMMITTEE IN CHARGE Chairman: I.McT. Cowan N. B a r t l e t t ^ W. R. Cullen A. V. Bree L. D. Hall P. R. Critchlow J . P. Kutney C. Reid External Examiner: F. G. A. Stone School of Chemistry University of B r i s t o l B r i s t o l 8, England REACTIONS OF SOME UNSATURATED FLUOROCARBON DERIVATIVES WITH ORGANO COMPOUNDS OF ARSENIC, SILICON, GERMANIUM AND TIN ABSTRACT Hexafluoroacetone r e a d i l y adds to primary and secondary arsines to form arsino-1,1,1,3,3,3-hexafluoro-propanols and to tetramethyldiarsine to form a moderately stable 1:1 complex at "20° . Trimethylarsine affords a 1:1 complex with hexafluoroacetone at 0 P although the complex i s completely dissociated at 20°. Trimethylsi-lahe, trimethylgermane, and t r i m e t h y l t i n hydride react with hexaf luoroacetone to form 1,1,1, 3, 3, 3",-hexaf luoro-propoxy derivatives and to d i a l k y l t i n dihydrides to form the bis(hexafluoropropoxy) d e r i v a t i v e s . Addition of a second mole of hexafluoroacetone to form 1:1 complexes with propoxygermane and propoxysilane occurs at 20°in the presence of excess hexafluoroacetone. The analogous 1:1 t i n complex can be i s o l a t e d and i s stable at 25°. Dimethylbis (1,1,1 ,-3, 3, 3-hexaf luoropropoxy) t i n gives a stable complex containing two moles of hexafluoroacetone. The structures of the arsine- and Group IV- hexafluoro-acetone complexes and some of t h e i r reactions are discussed. The f l u o r o c y c l o o l e f i n s , perfluorocyclobutene and 1,2-dichlorotetrafluorocyclobutene react with secondary arsines to give arsinocyclobutene d e r i v a t i v e s . Per-fluorocyclobutene affords the 1:1 adduct when heated with t r i m e t h y l s i l a n e and trimethylgermane. Trim e t h y l t i n hydride adds to perfluorocyclobutene at 20°to form the 1:1 adduct'which subsequently slowly decomposes to t r i m e t h y l t i n f l u o r i d e . ' The reaction-of Group IV hydrides with 1., 2-dich l o r o t e t r a f luorocyclobutene affords a number of products the nature of which varies with the Group IV metal or metalloid. Thus the reaction of the dichloro-cyclobutene with t r i e t h y l t i n hydride gives only t r i e t h y l -t i n chl or i.de, with t r i m e t h y l s i l a n e c h l o r o t r i m e t h y l s i -lane and 1-chlorotetraf luorocycl.obutyl-2-trimethylsilane are obtained,and with trimethylgermane reaction gives a var i e t y of cyclobutenyl and cyclobutylgermanes as well as chlorotrimethylgermane. . The configuration and con-formation of the cyclobutyl derivatives of the Group IV elements are established from, an analysis of t h e i r ^H n.m.r. spectra. Hexafluorobut-2-yne adds q u a n t i t a t i v e l y to t i n hydrides at 20° to afford the 1,1 31,4,4,4-hexafluoro-butenyl d e r i v a t i v e s . Hexamethylditin, tetraki.s ( t r i - • f luoromethyl)diarsi.ne, t r i m e t h y l s i l a n e and t r i e t h y l -germane add to hexafluorobut-2-yne on u l t r a v i o l e t i r r a d i a t i o n to give 1:1 adducts. The 1:1 trimethyl-silane-hexafluorobut-2-yne adduct also forms at 235 . Trimethyltin hydride and 1,1,1,-trifluoropropyne react slowly at 20 c to afford the 1:1. adduct. A study of the isomer d i s t r i b u t i o n of the 1:1 acetyl.ene adducts i n d i -cates i n a l l .cases a predominant formation of the trans isomer. Trimethylsilane catalyzes the conversion of trans-1,1,1,4,4,4-hexafl.uorobutenyltrimethylsilane to the cis-isomer and t r i m e t h y l t i n hydride catalyzes the conversion of c i s - 1 , 1 , 1 - t r i f l u o r o p r o p e n y l - 3 - t r i m e t h y l t i n to the trans-isomer. The diadducts^ (CH3) -jSiCHCF3-CH(CF3)Si(CH3) 3 and ((CH3)3Sn)2CHCH2CF3, are also obtained simultaneously with the formation of the re-spective 1:1 adducts although they are not formed by addition of the hydrides to the 1:1. adducts. GRADUATE STUDIES F i e l d of Study: Chemistry Topics i n Physical Chemistry Seminar i n Chemistry Chemical Thermodynamics Topics i n Inorganic Chemistry Advanced Inorganic Chemistry Spectroscopy and Molecular Structure Chemical. K i n e t i c s C r y s t a l Structures The Chemistry of Organometallie Compounds Topics i n Organic Chemistry A. Bree -J. R. Coope W. A. Bryce J. Butler N. B a r t l e t t H. C. Clark W. R. Cullen W. R. Cullen H. C. Clark A. .V..Bree. K. B. Harvey L. W. Reeves D. G. L. James N. B a r t l e t t S. Melzak J. Trotter H. C. Clark J . P. Kutney F. McCapra A. I. Scott PUBLICATIONS W. R. CULLEN and G. E, STYAN. Complex Formation by Hexafluoroacetone. Part I. Group IV Hydrides, Inorg, Chem., In press. W. R. CULLEN and G. E. STYAN. Reaction of Hexa-fluoroacetone with Arsines. J . Organometal. Chem., In press. Wo. R. CULLEN, D. S. DAWSON, and G. E. STYAN. Some Reactions of Hexafluorobut-2-yne with Compounds of Arsenic and Ti n . J . Organometal. Chem., J3, 406 (1965). W. R. CULLEN, D. S. DAWSON, P. S. DHALIWAL and G. E. STYAN. l-Dimethylarsino-2-chlorotetra-fluorocyclobutene and Related Compounds. Ind. (London), p. 502 (1964) . W, R. CULLEN, D. S. DAWSON, N. K. HOTA and G. E. STYAN. Some New Derivatives of Dimethylarsine. Chem. Ind. (London), p. 98.3 (1963). R E A C T I O N S OF SOME U N S A T U R A T E D FLUOROGARBON D E R I V A T I V E S WITH ORGANO COMPOUNDS OF A R S E N I C , S I L I C O N , GERMANIUM AND T I N b y G A R R I C K E. S T Y A N B . S c . ( H o n . ) , U n i v e r s i t y o f B r i t i s h C o l u m b i a , 1962 A T H E S I S S U B M I T T E D I N P A R T I A L F U L F I L M E N T OF THE R E Q U I R E M E N T S FOR THE DEGREE OF DOCTOR OF P H I L O S O P H Y i n t h e D e p a r t m e n t . o f C h e m i s t r y We a c c e p t t h i s t h e s i s a s c o n f o r m i n g t o t h e r e q u i r e d s t a n d a r d T H E U N I V E R S I T Y OF B R I T I S H C O L U M B I A May 1965 In p r e s e n t i n g t h i s t h e s i s i n p a r t i a l f u l f i l m e n t of the requirements f o r an advanced degree at the U n i v e r s i t y of • B r i t i s h Columbia, I agree that the L i b r a r y s h a l l make i t f r e e l y a v a i l a b l e f o r reference and study, I f u r t h e r agree that per-m i s s i o n f o r extensive copying of t h i s t h e s i s f o r s c h o l a r l y purposes may be granted by the Head of my Department or by h i s r e p r e s e n t a t i v e s . I t i s understood that, copying or p u b l i -c a t i o n of t h i s t h e s i s f o r f i n a n c i a l gain s h a l l not be allowed without my w r i t t e n permission* Department of Chemistry The U n i v e r s i t y of B r i t i s h Columbia, Vancouver 8, Canada Date June 25, 1965 i A B S T R A C T H e x a f l u o r o a c e t o n e r e a d i l y a d d s t o p r i m a r y a n d s e c o n d a r y a r -s i n e s t o f o r m a r s i n o - 1 , 1 , 1 , 3 , 3 , 3 - h e x a f l u o r o p r o p a n o 1 s a n d t o t e t -r a m e t h y l d i a r s i n e t o f o r m a m o d e r a t e l y s t a b l e 1:1 c o m p l e x a t 20°. T r i m e t h y l a r s i n e a f f o r d s a 1:1 c o m p l e x w i t h h e x a f l u o r o a c e t o n e a t o o 0 a l t h o u g h t h e c o m p l e x i s c o m p l e t e l y d i s s o c i a t e d a t 20 . T r i -m e t h y l s i l a n e , t r i m e t h y l g e r m a n e , a n d t r i m e t h y l t i n h y d r i d e r e a c t w i t h h e x a f l u o r o a c e t o n e t o f o r m 1,1,1,3, 3 , 3 - h e x a f l u o r o p r o p o x y d e r -i v a t i v e s a n d t o d i a l k y l t i n d i h y d r i d e s t o f o r m t h e b i s ( h e x a f l u o r o -p r o p o x y ) ' d e r i v a t i v e s . A d d i t i o n o f a s e c o n d m o l e o f h e x a f l u o r o -a c e t o n e . t o f o r m 1:1 c o m p l e x e s w i t h p r o p o x y g e r m a n e a n d p r o p o x y s i l a n e o c c u r s a t 20° i n t h e p r e s e n c e o f e x c e s s h e x a f l u o r o a c e t o n e . T h e a n a l o g o u s 1:1 t i n c o m p l e x c a n b e i s o l a t e d a n d i s s t a b l e a t 25°. D i m e t h y l b i s ( 1 , 1 , 1 , 3 , 3 J 3 - h e x a f l u o r o p r o p o x y ) t i n g i v e s a s t a b l e c o m p -l e x c o n t a i n i n g t w o m o l e s o f h e x a f l u o r o a c e t o n e . T h e s t r u c t u r e s o f t h e a r s i n e - a n d G r o u p I V - h e x a f l u o r o a c e t o n e c o m p l e x e s a n d some o f t h e i r r e a c t i o n s a r e d i s c u s s e d . T h e f l u o r o c y c l o b ' l e f i n s , p e r f l u o r o c y c l o b u t e n e : a n d 1 , 2 - d i c h l o r o -t e t r a f l u o r o c y c l o b u t e n e ' r e a c t w i t h s e c o n d a r y a r s i n e s t o g i v e a r s i n o -c y c l o b u t e n e d e r i v a t i v e s . P e r f l u o r o c y c l o b u t e n e a f f o r d s t h e 1:1 a d -d u c t w h e n h e a t e d w i t h t r i m e t h y l s i l a n e ' ©rd t r i m e t h y l g e r m a n e . T r i -o m e t h y l t i n h y d r i d e a d d s t o p e r f l u o r o c y c l o b u t e n e a t 20 t o f o r m t h e 1:1 a d d u c t w h i c h s u b s e q u e n t l y s l o w l y d e c o m p o s e s t o t r i m e t h y l t i n f l u o r i d e . T h e r e a c t i o n o f G r o u p I V h y d r i d e s w i t h 1 , 2 - d i c h l o r o -t e t r a f l u o r o c y c l o b u t e n e a f f o r d s a n u m b e r o f p r o d u c t s t h e n a t u r e o f w h i c h v a r i e s w i t h t h e G r o u p I V m e t a l o r m e t a l l o i d . T h u s t h e r e a c -t i o n o f t h e d i c h l o r o c y c l o b u t e n e w i t h t r i e t h y l t i n h y d r i d e g i v e s o n l y t r i e t h y l t i n c h l o r i d e , w i t h t r i m e t h y l s i l a n e c h l o r o t r i m e t h y l s i 1 -a n e a n d 1 - c h l o r o t e t r a f l u o r o c y c l o b u t y 1 - 2 - t r i m e t h y l s i l a n e a r e o b t a i n e d i i a n d w i t h t r i m e t h y 1 g e r m a n e r e a c t i o n g i v e s a v a r i e t y o f c y c l o b u t e n y l a n d e y e l o b u t y l g e r m a n e s a s w e l l a s c h l o r o t r i m e t h y l g e r m a n e . T h e c o n f i g u r a t i o n a n d c o n f o r m a t i o n o f t h e e y e l o b u t y 1 d e r i v a t i v e s o f t h e G r o u p I V e l e m e n t s a r e e s t a b l i s h e d f r o m a n a n a l y s i s o f t h e i r *H n.m.r. s p e c t r a . o H e x a f l u o r o b u t - 2 - y n e a d d s q u a n t i t a t i v e l y t o t i n h y d r i d e s a t 20 t o a f f o r d t h e 1,1, 1,14.,I4.,i\.-hexafluorobuteny 1 d e r i v a t i v e s . H e x a -m e t h y l d i t i n , t e t r a k i s ( t r i f l u o r o m e t h y 1 ) d i a r s i n e , t r i me t h y I s i l a n e a n d t r i e t h y l g e r m a n e a d d t o h e x a f l u o r o b u t - 2 - y n e o n u l t r a v i o l e t i r -r a d i a t i o n t o g i v e 1:1 a d d u c t s . T h e 1:1 t r i m e t h y 1 s i l a n e - h e x a f l u o r o b u t - 2 - y n e a d d u c t a l s o f o r m s a t 235°• T r i m e t h y l t i n h y d r i d e a n d 1,1 t r i f l u o r o p r o p y n e r e a c t s l o w l y a t 20° t o a f f o r d t h e 1:1 a d d u c t . A s t u d y o f t h e i s o m e r d i s t r i b u t i o n o f t h e 1:1 a c e t y l e n e a d d u c t s i n d -i c a t e s i n a l l c a s e s a p r e d o m i n a n t f o r m a t i o n o f t h e t r a n s - i s o m e r . . T r i m e t h y l s i l a n e c a t a l y z e s t h e c o n v e r s i o n o f t r a n s - 1, 1, 1, h,, l±, lj.-h.exa f l u o r o b u t e n y I t r i m e t h y 1 s i l a n e t o t h e c i s - i s o m e r a n d t r i m e t h y l t i n h y d r i d e c a t a l y z e s t h e c o n v e r s i o n o f c_ i _ s - 1, 1, 1 - t r i f l u o r o p r o p e n y 1-3 -t r i m e t h y l t i n t o t h e t r a n s - i s o m e r . T h e d i a d d u c t s , ( C H ^ ) ^ S i C H C F ^ -O H t C F ^ S i ( C H ^ ) ^ a n d ( ( C H ^ ) g C H C H g C F a r e a l s o o b t a i n e d s i m u l t -a n e o u s l y w i t h t h e f o r m a t i o n o f t h e r e s p e c t i v e 1:1 a d d u c t s a l t h o u g h t h e y a r e n o t f o r m e d b y a d d i t i o n o f t h e h y d r i d e s t o t h e 1:1 a d d u c t s T A B L E OF CONTENTS A B S T R A C T ACKNOWLEDGEMENTS L I S T OF F I G U R E S L I S T OF T A B L E S H G E N E R A L I N T R O D U C T I O N C H A P T E R I . H E X A F L U O R O A C E T O N E I N T R O D U C T I O N E X P E R I M E N T A L A. A p p a r a t u s a n d T e c h n i q u e s B. R e a c t i o n o f A r s i n e s w i t h H e x a f l u o r o a c e t o n e (1) S y n t h e s i s o f S t a r t i n g M a t e r i a l s (2) R e a c t i o n w i t h H e x a f l u o r o a c e t o n e C. R e a c t i o n o f G r o u p I V H y d r i d e s w i t h H e x a f l u o r o a c e t o n e (1) S y n t h e s i s o f S t a r t i n g M a t e r i a l s (2) R e a c t i o n w i t h H e x a f l u o r o a c e t o n e D I S C U S S I O N A . A r s i n e s (1) R e s u l t s (2) P r o p o s e d M e c h a n i s m s a n d S t r u c t u r e s B. G r o u p I V H y d r i d e s ( 1) R e s u l t s (2) P r o p o s e d M e c h a n i s m s a n d S t r u c t u r e s C H A P T E R I I . . P E R F L U O R O C Y C L O B U T E N E AND 1, 2 - D I C H L O R O T E T R A F L U O R O C Y C L O B U T E N E I N T R O D U C T I O N E X P E R I M E N T A L A. A r s i n e s (1) S t a r t i n g M a t e r i a l s (2) R e a c t i o n s w i t h t h e G y c l o b u t e n e s (3) *H n.m.r. S t u d i e s o f D i m e t h y l a r s i n e a n d t h e F l u o r o c y c l o b u t e n e s a t 20° B. G r o u p I V H y d r i d e s (1) S t a r t i n g M a t e r i a l s (2) R e a c t i o n s w i t h t h e C y c l o b u t e n e s D I S C U S S I O N A. A r s i n e s (1) R e s u l t s (2) P r o p o s e d M e c h a n i s m s B. G r o u p I V H y d r i d e s ; (1) R e s u l t s (2) *H n.m.r. S p e c t r a (3) P r o p o s e d M e c h a n i s m s C H A P T E R I I I . F L U O R O A C E T Y L E N E S I N T R O D U C T I O N E X P E R I M E N T A L A. G r o u p I V H y d r i d e s i v (1) S t a r t i n g M a t e r i a l s 8 l (2) R e a c t i o n s w i t h F l u o r o a c e t y l e n e s 82 B. M e t a l - M e t a l B o n d s 89 (1) S t a r t i n g M a t e r i a l s 89 (2) R e a c t i o n s w i t h H e x a f l u o r o b u t - 2 - y n e 9 0 D I S C U S S I O N - 91+ A. G r o u p I V H y d r i d e s 9l+ (1) R e s u l t s 9 i i (2) P r o p o s e d M e c h a n i s m s 10I4. B. M e t a l - M e t a l B o n d s 110 (1) R e s u l t s 111 (2) P r o p o s e d M e c h a n i s m s 113 R E F E R E N C E S 11-5 V L I S T OF F I G U R E S F i g u r e 1. *H n.m.r. S p e c t r u m o f a 1:2 H e x a f l u o r o a c e t o n e - 1,1,1 3 » 3 , 3 - H e x a f l u o r o p r o p o x y t r i m e t h y l g e r m a n e M o l a r M i x t u r e 2. *H n.m.r. S p e c t r u m o f l , 2 - D i c h l o r o - 3 , 3 i U > U - t e t r a -f l u o r o c y c l o b u t y l t r i m e t h y l g e r m a n e 3 . *H n.m.r. S p e c t r u m o f 1 - H - H e x a f l u o r o c y c l o b u t y 1 - 2 -t r i m e t h y 1 g e r m a n e I;'. *H n . m . r . S p e c t r u m o f 1 - H - H e x a f l u o r o c y c l o b u t y 1 - 2 -t r i m e t h y l t i n 5 . *H n.m.r. S p e c t r u m o f 1:1 T r i m e t h y l t i n H y d r i d e - 1 , 1 , 1 6 . *H n.m.r. S p e c t r u m o f 1:1 D i m e t h y l a r s i n e - 1 , 1 , 1 - T r i -T r i f l u o r o p r o p y n e A d d u c t s : f l u o r o p r o p y n e A d d u c t s L I S T OF T A B L E S T a b l e I . I n f r a r e d S p e c t r a o f 1 , 1 , 1 , 3 , 3 , 3 ~ H e x a f l u o r o p r o p o x y D e r i v a t i v e s 1 19 I I . Some H a n d F C h e m i c a l S h i f t s a n d C o u p l i n g C o n s t -I l l a n t s o f 1 , 1 , 1 , 3 , 3 > 3 - H e x a f l u o r o p r o p o x y D e r i v a t i v e s 2 H C h e m i c a l S h i f t s o f (CH-> ^  S n(OCH(CF_.) p ) ? a n d ( C H 3 ) 2 S n ( O C H ( C F 3 ) 2 ) 2 - 2 ( C F 3 ) 2 CO S o l u t i o n ^ I V . D a t a C o n c e r n i n g H e x a f l u o r o b u t y 1 D e r i v a t i v e s . V.. H-F C o u p l i n g C o n s t a n t s o f t h e 1:1 F l u o r o c y c l o b u t e n e H y d r i d e A d d u c t s V I . D a t a C o n c e r n i n g H e x a f l u o r o b u t e n y 1 D e r i v a t i v e s V I I . Some C h a r a c t e r i s t i c I n f r a r e d A b s o r p t i o n s o f t h e . 1, 1, 1, l i , l | , l + - H e x a f l u o r o b u t e n y 1 D e r i v a t i v e s V I I I . F o r m a t i o n o f 1:1 a n d 1:2 T r i m e t h y l s i l a n e - B u t y n e A d d u c t s I X . R e a c t i o n o f ; T r i m e t h y l t i n H y d r i d e a n d 1 , 1 , 1 - T r i f l u o r o p r o p y n e v i ACKNOWLEDGEMENTS I f e e l v e r y m u c h i n d e b t e d t o D r . W. R. C u l l e n f o r h i s s u p e r -v i s i o n a n d f o r h i s h o n e s t y i n a s s i g n i n g a n d s u g g e s t i n g r e s e a r c h t o p i c s . My a s s o c i a t i o n w i t h h i m h a s b e e n p l e a s a n t , i n s t r u c t i v e , a n d , I b e l i e v e , v e r y p r o d u c t i v e . I t h a n k D r . L. 'D. H a l l f o r d e v o t i n g h i s t i m e t o o b t a i n t h e 19 1 F n . m . r . s p e c t r a a n d f o r h i s a i d i n s o l v i n g t h e H n . m . r . s p e c t r a o f t h e c y c l o b u t a n e s y s t e m s i n C h a p t e r I I . T h r o u g h o u t my g r a d u a t e w o r k t h e N a t i o n a l R e s e a r c h C o u n c i l o f C a n a d a h a s a w a r d e d me a B u r s a r y ( 1962-1963) a n d S t u d e n t s h i p s ( 1963-1965) w h i c h a r e g r a t e f u l l y a c k n o w l e d g e d . 1 G E N E R A L I N T R O D U C T I O N T h e s t u d y o f t h e r e a c t i o n s o f u n s a t u r a t e d o r g a n i c c o m p o u n d s , p a r t i c u l a r l y ' o l e f i n s , w i t h o r g a n o m e t a 1 1 i c c o m p o u n d s w a s g r e a t l y s t i m u l a t e d by' t h e l a r g e d e m a n d s made f o r s t a b l e p o l y m e r i c m a t -e r i a l s , s u c h a s s y n t h e t i c r u b b e r , d u r i n g W o r l d War I I . T h e a d -d i t i o n o f o r g a n o m e t a 1 l i e c o m p o u n d s t o o l e f i n s w a s d i s c o v e r e d m o r e t h a n t h i r t y - f i v e y e a r s a go*>2 b u t t h e g r e a t e s t c o m m e r c i a l i m p e t u s w a s s u p p l i e d b y Z i e g l e r a n d c o w o r k e r s i n 1950^ who f o u n d t h a t e t h y l e n e c o u l d b e p o l y m e r i z e d b y l i t h i u m a l k y l s , LiC.oH,- + n C nH,. » L i £ c H 0 C H 2 1 X5 T " " 2 J l U ~ " L 1 L U I 2 W 1 2 n C 2 H 5 a n d i n 1 9 5 2 ^ t h e s e same w o r k e r s d i s c o v e r e d a n a n a l o g o u s p o l y -m e r i z a t i o n o f e t h y l e n e b y t r i a l k y l a l u m i n u m c o m p o u n d s . V l R + n C~H,, —> V A 1 f H 2 C H 2 J n R T h e s u p e r i o r h i g h t e m p e r a t u r e p r o p e r t i e s o f o r g a n o s i l i -% 6 c o n e s ^ a n d t h e u n e x p e c t e d h i g h s t a b i l i t y o f f e r r o c e n e l e d t o a n i n t e r e s t i n t h e i n c o r p o r a t i o n o f o r g a n o m e t a 1 1 i c c o m p o u n d s i n t o p o l y m e r i c m a t e r i a l s . .The h i g h t h e r m a l s t a b i l i t y a n d g e n -e r a l i n e r t n e s s o f f l u o r o c a r b o n s r e l a t i v e t o t h e i r h y d r o c a r b o n a n a l o g u e s l e d t o t h e i r a p p l i c a t i o n a s r e f i g e r a n t s i n 1928 a n d l a t e r t o t h e i r u s e a s p r o p e l l a n t s i n t h e a e r o s o l i n d u s t r y . T h e l a r g e p r o d u c t i o n o f f l u o r o c a r b o n s f o r t h e s e t w o b a s i c a p p l i c a -7 t i o n s n e c e s s a r i l y l e d . t o t h e d e v e l o p m e n t o f b y - p r o d u c t s . T h e u s e o f f l u o r o b ' l e f i n s a s i n t e r m e d i a t e s f o r , p o l y m e r i c m a t e r i a l s s u c h a s r e s i n s , e l a s t o m e r s a n d p l a s t i c s h a s b e c o m e a n i m p o r t a n t o u t l e t f o r f l u o r o c a r b o n c h e m i c a l s . T h e c o m m e r c i a l a v a i l a b i l i t y o f f l u o r o o l e f i n s a n d f l u o r o -a c e t y l e n e s h a s a l l o w e d f o r n u m e r o u s i n v e s t i g a t i o n s o f t h e r e a c -t i o n s o f t h e s e f l u o r o c a r b o n s w i t h o r g a n o m e t a 1 1 i c c o m p o u n d s . T h e r e i s a c o n s i d e r a b l e c o m m e r c i a l i n t e r e s t i n t h e r e a c t i o n 2 p r o d u c t s a s i n t e r m e d i a t e s f o r p o l y m e r f o r m a t i o n , p a r t i c u l a r l y f l u o r o b r g a n o s i 1 i c o n e s w h i c h m i g h t be e x p e c t e d t o c o m b i n e t h e t h e r -m a l s t a b i l i t y o f s i l o x a n e s w i t h t h e r e s i s t a n c e t o s o l v e n t s o f f i u o r o c a r b o n s . T h e r e a c t i o n s ; o f : f l u o r o o l e f i n s w i t h s i l a n e s ^ ' ^ ' 1 1 1 2 1 "5 . . i . t i n h y d r i d e s ' a n d t r a n s i t i o n m e t a l s J h a v e b e e n o f r e c e n t i n t e r e s t . T h e i n i t i a l i n t e r e s t i n f I u o r o c a r b o n s w a s due t o t h e i r h i g h t h e r m a l s t a b i l i t y a n d g e n e r a l i n e r t n e s s . H o w e v e r , t h e h i g h e l -e c t r o n e g a t i v i t y o f - f l u o r i n e d o e s n o t a l w a y s r e s u l t in.,, a n o v e r a l l d e c r e a s e i n a c t i v i t y , , a n d s u b s t i t u t i o n o f f l u o r o a l k y l g r o u p s f o r a l k y l g r o u p s c a n g i v e r i s e t o an. e x t r e m e l y r e a c t i v e m o l e c u l e . T h e f i r s t c h a p t e r o f t h i s t h e s i s i s ' c o n c e r n e d w i t h o n e s u c h m o l -e c u l e , h e x a f l u o r o a c e t o n e . A r e c e n t r e v i e w ^ s u b s t a n t i a l l y c o v - ; e r s t h e r e a c t i o n s o f p e r f l u o r o k e t o n e s w i t h o r g a n i c c o m p o u n d s , b u t l i t t l e i n f o r m a t i o n i s a v a i l a b l e r e g a r d i n g t h e r e a c t i o n s o f p e r f l u o r o . k e t o n e s w i t h o r g a n o m e t a 11 i c c o m p o u n d s o t h e r t h a n G r i g -n a r d r e a g e n t s . T h e s e c o n d c h a p t e r o f t h i s , t h e s i s i n v o l v e s t h e i n v e s t i g a t i o n o f t h e r e a c t i o n s o f some c y c l i c f l u o r o o 1 e f i n s p e r f l u o r o c y c l o b u t -e n e , 1 , 2 - d i c h l o r o t e t r a f l u o r o c y c l o b u t e n e , a n d 1 , 2 - d i c h l o r o h e x a -f l u o r o c y c l o p e n t e n e . T h e r m o c h e m i c a l d a t a c o n c e r n i n g t h e c h l o r -i n a t i o n o f f l u o r o o l e f i n s - - t h e e n t h a l p y o f c h l o r i n a t i o n o f p e r -f l u o r o c y c 1 o b u t e n e (,cxtl - — 37 -U- k c a l / m o l e ) i s 20 k c a l / m o l e g r e a t e r t h a n t h a t o f t e t r a f l u o r o e t h y l e n e ( A H = -5>7«3 k c a l / m o l e ) --dem-o n s t r a t e s t h a t p e r f l u o r o c y c l o b u t e n e s h o u l d b e a p a r t i c u l a r l y i n t e r e s t i n g ' i n t e r m e d i a t e f o r t h e f o r m a t i o n o f v i n y l d e r i v a t i v e s . T h e p r e p a r a t i o n o f s u c h v i n y l s i l a n e s f r o m c y c l i c f l u o r o o l e f i n s 8 h a s b e e n w e l l i n v e s t i g a t e d i n a U.S. p a t e n t . 3 T h e t h i r d c h a p t e r o f t h i s t h e s i s d e a l s p r e d o m i n a n t l y w i t h some r e a c t i o n s o f h e x a f l u o r o b u t - 2 - y n e . W h e r e a s t h e e f f e c t o f t h e t r i f l u o r o m e t h y 1 g r o u p s o n t h e c a r b o n y l g r o u p i n h e x a f l u o r o -a c e t o n e - e n h a n c e s i t s r e a c t i v i t y , t h e i n d u c t i v e e f f e c t o f t h e t r i -f l u o r o m e t h y l g r o u p s o n t h e t r i p l e b o n d i n h e x a f l u o r o b u t - 2 - y n e makes i t m o r e s u s c e p t i b l e t o n u c l e o p h i l i c a t t a c k b u t l e s s s u s -c e p t i b l e t o e l e c t r o p h i 1 i c a t t a c k t h a n i t s h y d r o g e n a n a l o g u e , b u t - 2 - y n e . T h e r e h a s b e e n c o n s i d e r a b l e i n t e r e s t i n t h e r e a c t i o n s o f h e x a f l u o r o b u t - 2 - y n e w i t h t r a n s i t i o n m e t a l c o m p o u n d s J ' C H A P T E R I H E X A F L U O R O A C E T O N E I N T R O D U C T I O N A l a r g e n u m b e r o f c o m p l e t e l y f l u o r i h a t e d k e t o n e s h a v e b e e n p r e p a r e d i n r e c e n t y e a r s ^  ' ^ ' . H e x a f l u o r o a c e t o n e w a s 17 p r e p a r e d f o r t h e f i r s t t i m e b y F u k u h a r a a n d B i g e l o w ' i n 19LL1. T h e s t r o n g e l e c t r o n w i t h d r a w a l e x e r t e d b y p o l y f l u o r o a I k y l g r o u p s a l p h a t o a c a r b o n y l g r o u p i s o b v i o u s f r o m t h e e a s e o f a d d i t i o n o f HX m o l e c u l e s t o t h e f u n c t i o n a l g r o u p ^ . T h u s t h e e q u i l i b r i u m r e a c t i o n R f 2 C = 0 + HX ^ — : R f COHX l i e s f a r , a n d o f t e n c o m p l e t e l y , . t o t h e r i g h t . T h e r e a c t i o n c o n -d i t i o n s n e c e s s a r y f o r t h e a d d i t i o n o f a w e a k n u c l e o p h i l e s u c h a s w a t e r a r e e x t r e m e l y m i l d , q u a n t i t a t i v e a d d i t i o n t a k i n g p l a c e a t l 8 19 21 r o o m t e m p e r a t u r e ' ' . A t l o w t e m p e r a t u r e s a d d i t i o n o f m i n -22 e r a l a c i d s ( X = F, C I , B r , I ) t o p e r f l u o r o c y c l p b u t a n o n e g i v e s h i g h y i e l d s of-o<-ha l o a l c o h o 1 s'. A n u m b e r o f o t h e r a c i d s h a v e 23 2l i b e e n a d d e d t o s i m i l a r f l u o r i n a t e d k e t o n e s t o 1 g i v e 1:1 a d d u c t s ' T h e f o r m a t i o n o f h e m i k e t a l s ( X = OR) w i t h f l u o r i n a t e d k e t o n e s h a s b e e n i n v e s t i g a t e d f a i r l y e x t e n s i v e l y b y S i m m o n s a n d W i l e y P r e v i o u s w o r k o n t h e r e a c t i o n s o f f l u o r i n a t e d k e t o n e s w i t h G r o u p V c o m p o u n d s h a s b e e n l a r g e l y c o n f i n e d t o t h e a d d i t i o n o f 26 2LL 2E? 2*7 t h e k e t o n e s t o t h e N-H b o n d s o f a m m o n i a , a m i n e s ' , a m i d e s 27 a n d u r e a s . I t w a s f o u n d t h a t p r i m a r y a m i d e s a n d p r i m a r y u r e a s w i l l f o r m 1:1 a d d u c t s w i t h f l u o r i n a t e d k e t o n e s b u t s e c o n d a r y a m i d e s , s e c o n d a r y u r e a s , t h i o a m i d e s a n d s u l p h o n a m i d e s a r e u n -27 r e a c t i v e . Some w o r k h a s b e e n d o n e o n t h e r e a c t i o n s o f f l u o r -2 1 , 2 8 i n a t e d k e t o n e s w i t h t r i a l k y l p h o s p h i t e s , - a n d i t w a s f o u n d t h a t t h e p r o d u c t s v a r y w i t h t h e k e t o n e a s i s s h o w n b y t h e f o l l o w i n g 5 e x a m p l e s : ( C 2 F ^ ) 2 C O '+ P ( ' 0 0^ ) 3 > C 2 F ^ C ( O C H 3 ) = C F C F 3 + F P ( O ) {CCH^) 2 ( C 1 C F 2 ) 2 C 0 + P ( O C 2 H 5 ) 3 > C 2 H ^ C 1 + ( C ^ Q ) 2 P (O) OC ( C F ^ 1) =CF 2 A d d i t i o n o f t h e s e k e t o n e s - t o t h e p h o s p h i t e s o c c u r s - u n d e r v e r y m i l d c o n d i t i o n s , f o r e x a m p l e " t h e h i g h l y r e a c t i v e p e r f l u o r o c y c l o b u t a n - 1 , 2-d i o n e a d d s t o t r i m e t h y l p h o s p h i t e a t - 7 0 ° . A d d i t i o n o f p e r f l u o r o -c y c l o b u t a n o n e t o p h o s p ' h i r i e o c c u r s i n t h e s a m e - m a n n e r a s a d d i t i o n , 29 t o a m i n e s . PH ^ + ( C F 2 ) 3 C O ( C F 2 ) 3 C ( O H ) P H 2 + JjCF 2) 3 C O H J 2 P H T h e r a t i o o f t h e m o n o a d d u c t t o t h e d i a d d u c t v a ' r i e s w i t h t h e r a t i o o f t h e r e a c t a n t s . ' '' ' T h e o n l y p r e v i o u s l y r e p o r t e d r e a c t i o n i n v o l v i n g a G r o u p I V c o m p o u n d a n d a f l u o r i n a t e d k e t o n e i s t h e a d d i t i o n o f p . e r f l u o r o -29 e y e l o b u t a n o n e t o d i - n - b u t y l s i l a n e ( n - C , H') 0 S i H „ + 2 ( C F o ) . C 0 > ( n - C , H n ) o S i f 0 C H ( C F o ) ^ - 9 ' 2 0 i I 1 2 " " ^ - 2 ' f ^ v " - ^ i ^ , - 2 o i | ^ O C H ( C F 2 ) 2 2 N o t e t h a t t h e d i r e c t i o n o f a d d i t i o n i s d i f f e r e n t f r o m a c i d a n d 29 G r o u p V a d d i t i o n i n t h a t n o OH g r o u p i s f o r m e d . P a r s h a l l a l s o f o u n d t h a t p e r f l u o r o c y c l o b u t a n o n e r e a c t s w i t h b o t h b o r o r i t r i c h l o r - . i d e a n d p h e n y l d i c h l o r o b o r a n e i n a s i m i l a r m a n n e r . C 6 H ^ B C 1 2 + ( C F 2 ) 3 C O > G 6 H ^ B J 0 C C 1 ( C F 2 ) J [ 2 B C 1 3 + ( C F ' 2 ) 3 C O > B J O : C l ( C F 2 ) ^ J 5 Some r e a c t i o n s o f h e x a f l u o r o a c e t o n e w i t h G r o u p I V a n d G r o u p V o r g a n o m e t a 1 1 i c c o m p o u n d s h a v e b e e n s t u d i e d i n t h e p r e s e n t i n v e s t -i g a t i o n , a n d t h e r e s u l t s a r e p r e s e n t e d i n t h e f o l l o w i n g d i s c u s s i o n a n d e x p e r i m e n t a l s e c t i o n s . 6 E X P E R I M E N T A L • . • A. A p p a r a t u s a n d T e c h n i q u e s T h e f o l l o w i n g d e s c r i p t i o n w i l l c o v e r t h e a p p a r a t u s a n d g e n -e r a l t e c h n i q u e s u s e d f o r t h e e x p e r i m e n t a l w o i r k d e s c r i b e d i n t h i s t h e s i s i n a l l t h r e e c h a p t e r s , ; H e x a f l u o r o a c e t o n e , C y c l o b u t e n e s , a n d F l u o r o a l k y n e s . R e a c t a n t s a n d p r o d u c t s w e r e m a n i p u l a t e d u s i n g s t a n d a r d v a c u u m t e c h n i q u e s . E x c e p t ' w h e r e o t h e r w i s e i n d i c a t e d , v o l a t i l e m a t e r i a l s w e r e p u r i f i e d b y t r a p - t o - t r a p d i s t i l l a t i o n u s i n g s u i t a b l e l o w t e m p e r a t u r e b a t h s ' t o c o o l t h e t r a p s . R e a c t i o n s w e r e c a r r i e d o u t i n t h i c k - w a l l e d : P y r e x t u b e s . , F o r r e a c t i o n s , i n i t i a t e d b y u l t r a -v i o l e t i r r a d i a t i o n t h e P y r e x C a r i u s t u b e c o n t a i n i n g t h e r e a c t a n t s .was p l a c e d 30 t o I4.O cm f r o m ; t h e l i g h t s o u r c e . P y r e x e f f e c t i v e l y a b s o r b s a n y u l t r a v i o l e t r a d i a t i o n b e low; 3 0 0 0.A. ; W h e r e n e c e s s a r y ' n o n - v o l a t i l e m a t e r i a l s w e r e , m a n i p u l a t e d , i n a n i n e r t a t m o s p h e r e c h a m b e r . M o l e c u l a r w e i g h t s w e r e m e a s u r e d b y R e g n a u l t ' s m e t h o d e ' x c e p t w h e r e o t h e r w i s e i n d i c a t e d . F o r t h e p r e p a r a t i o n o f t h e v o l a t i l e h y d r i d e s ( a r s i n e s , ; g e r -m a n e s a n d t i n h y d r i d e s ) t h e e x p e r i m e n t a l s e t - u p d e s c r i b e d by, J o l l y 30 a n d D r a k e ' w a s u s e d w i t h l i t t l e o r n o m o d i f i c a t i o n . . A n A e r o g r a p h , m o d e l A - 9 0 - P , w a s u s e d f o r v . p . c . a n a l y s i s . T h e c h r o m a t o g r a p h i c c o l u m n s : w e r e o f t w o s i z e s , - x | " a n d 10' x \ " . T h e f l o w r a t e s n o r m a l l y v a r i e d f r o m 2 t o 15 c c / m i n . w i t h e i t h e r h e l i u m o r n i t r o g e n a s t h e c a r r i e r g a s . S e p a r a t i o n s w e r e made w i t h ' t h e i n j e c t o r a p p r o x i m a t e l y 2 5 ° a b o v e , a n d t h e d e t e c t o r 3 5 ° a b o v e , t h e c o l u m n t e m p e r a t u r e . -1 I n f r a r e d s p e c t r a r e p o r t e d i n c m w e r e r u n o h a P . E . 21 i n s t r u m e n t , t h o s e r e p o r t e d i n m i c r o n s w e r e r u n : o n a c a l i b r a t e d 19 1 P . E . 137. T h e F a n d H n . m . r . s p e c t r a w e r e o b t a i n e d w i t h a 7 V a r i a n H.R. 60 ( a t 56«4" M c / s ) a n d A - 6 0 s p e c t r o m e t e r s . U n l e s s 19 o t h e r w i s e i n d i c a t e d F s p e c t r a a r e r e p o r t e d i n p.p.m. r e l a t i v e t o e x t e r n a l t r i f l u o r o a c e t i c a c i d a n d s p e c t r a i n p.p.m. r e l -a t i v e t o e x t e r n a l t ' e t r a m e t h y l s i l a n e r e f e r e n c e s ( n e g a t i v e v a l u e s t o l o w f i e l d s i d e ) . M i c r o a n a l y s e s , w e r e c a r r i e d o u t b y D r . A l f r e d B e r n h a r d t , Mu l h e i m , .'Germany ( a r s e n i c ' a n d s i 1 i c o n c o m p o u n d s ) a n d b y t h e S c h w a r t z k o p f M i c r o a n a l y t i c a 1. L a b o r a t o r y , W o o d s i d e 77» N.Y., U . S.A. ( t i n a n d g e r m a n i u m c o m p o u n d s ) . ' M i c r o a n a l y s e s . . i n w h i c h o n l y t h e c a r b o n a n d h y d r o g e n a r e r e p o r t e d w e r e c a r r r e d o u t b y M r s . C. J e n k i n s , D e p a r t m e n t o f C h e m i s t r y , . U n i v e r s i t y ' of. B r i t i s h C o l u m b i a . .: B . R e a c t i o n o f A r s i.nes w i t h H e x a f l u o r o a c e t o n e ( 1) S y n t h e s i s o f S t a r t i n g , M a t e r i a l s T h e h e x a f l u o r o a c e t o n e ( H . F . A . ) w a s k i n d l y s u p p l i e d b y G e n -e r a l C h e m i c a l D i v i s i o n , A l l i e d C h e m i c a l C o r p o r a t i o n , U . S . A : a n d w a s p u r i f i e d b y t r a p - t o - 1 r a p d i s t i 1 1 a t i o n • (mo 1.. w t . F o u n d : 166; C a l c : 1 6 6 ) . ( a ) , T e t r a m e t h y l d i a r s i n e - - T h e d i a r s i n e . ( c a c o d y l ) w a s p r e p a r e d b y t h e r e d u c t i o n o f d i m e t h y l a r s i n i c a c i d w i t h e x c e s s h y p o p h o s -31 p h o r . o u s a c i d i n 2.5N h y d r o c h l o r i c a c i d . T h e d i a r s i n e w a s d i s t -i l l e d u n d e r r e d u c e d p r e s s u r e , b . p . 7'4-° (LL6 mm). I t s p u r i t y w a s c h e c k e d b y *H n . m . r . w h i c h s h o w e d o n l y o n e p e a k a t - 1 . 1 3 p.p.m. T h e f o l l o w i n g v a p o u r , p r e s s u r e d a t a w e r e o b t a i n e d ' • f o r / t h e d i a r s i n e . T ° K p cm l o g p ^ x 1 0 3 ° K 292 0 . 2 5 - 0 . 6 0 2 3- i |2 3 0 9 . 5 1.25 +0.096 3 . 2 3 3 2 6 . 6 2 . 6 O.LL15 3 . 0 6 3 3 6 . 8 • , . 3 . 9 0 . 5 9 1 2 . 9 7 3 5 0 . 8 6 . 8 0 . 8 3 2 2 . 8 5 3 6 1 . 5 9 . 9 5 0 . 9 9 8 2.77 37k 15.1 I.I . 7 8 2 . 6 ? 3 7 7 . 1 1 6 . 7 5 l .223 2 . 6 5 8 1 3 o • -1 T K p cm l o g p - ,x 1(K w K 3 8 8 . 3 2 3 . 6 5 1.373 2 .57 / 3 9 ^ . 8 2 8 . 7 1.^57 2 . 5 3 i+02.4 3 5 . 6 5 1.551 2 . 4 9 I+5.4 1.657 2.I+3 1+18.8 5 5 . 4 5 1-743 2 . 3 9 A l i n e a r p l o t o f l o g p a g a i n s t ^ w a s o b t a i n e d f o r t h e w h o l e r a n g e . T h i s w a s u s e d t o g i v e : b . p . = 1 5 8 . 4 + 0 . 2 ° a L v = 9 . 0 5 k c a l / m o l e T r o u t o n ' s c o n s t . = 2 2 . 1 e . u . ( b ) D i m e t h y I a r s i n e - - C h l o r o d i m e t h y l a r s i n e w a s p r e p a r e d b y t h e 31 33 r e d u c t i o n o f d i m e t h y l a r s i n i c a c i d W i t h h y p o p h o s p h o r o u s a c i d . T h e c h l o r o d i m e t h y l a r s i n e w a s d i s s o l v e d i n h y d r o c h l o r i c a c i d a n d w a s r e d u c e d b y a n a l c o h o l i c z i n c s o l u t i o n t o p r o d u c e d i m e t h y l a r s -i n e ^ . T h e d i m e t h y l a r s i n e w a s p u r i f i e d b y f i r s t s e a l i n g i t o f f i n a C a r i u s t u b e w i t h s o d i u m h y d r o x i d e a n d t h e n r e p e a t i n g t h i s p r o c e d u r e w i t h p h o s p h o r u s p e n t o x i d e . T h e i d e n t i t y a r i d p u r i t y w a s e s t a b l i s h e d b y i t s i n f r a r e d s p e c t r u m w h i c h s h o w e d a s t r o n g A s - H a b s o r p t i o n a t 4.8^( a n d b y i t s m o l e c u l a r w e i g h t o f 1 0 7 . 5 ( C a l c : 1 0 6 . 0 ) . T h e *H n . m . r . s p e c t r u m s h o w e d t w o s e t s o f p e a k s ; o n e , a d o u b l e t , c e n t e r e d a t -O . 8 7 p.p.m. ( J = 6 . 7 c p s ) a n d t h e o t h e r , a s e p t e t , c e n t e r e d a t - 2 . 2 9 p.p.m. ( J = 6 . 8 c p s ) o f r e l a -t i v e i n t e n s i t i e s 1 :5 .9 ( C a l c . 1 : 6 . 0 ) . ( c ) M e t h y l a r s i r i e - - D i c h l o r o m e t h y l a r s i n e w a s p r e p a r e d b y t h e 3 5 r e d u c t i o n o f m e t h y l a r s o n i c a c i d b y s u l p h u r d i o x i d e . D i c h l o r o -m e t h y l a r s i n e w a s r e d u c e d t o t h e c o r r e s p o n d i n g h y d r i d e b y t h e same p r o c e d u r e u s e d t o r e d u c e c h l o r o d i m e t h y l a r s i n e t o d i m e t h y l a r s ine^'-^'''. M e t h y l a r s i n e w a s p u r i f i e d i n t h e same m a n n e r d e s c r i b e d f o r d i m e t h y l -^ . . o 32 A b o i l i n g p o i n t o f 17,0 h a s b e e n r e p o r t e d . 9 a r s i n e . I t s i n f r a r e d s p e c t r u m s h o w e d a s t r o n g , b r o a d A s - H a b -s o r p t i o n a t 1+-75/I • I t s *H n.m . r . s p e c t r u m s h o w e d a t r i p l e t a t -O . 7 8 p.p.m. ( J = 7 . 2 c p s ) a n d a q u a r t e t a t - I . 8 3 p . p . n u ( J = 7-1 c p s ) o f r e l a t i v e i n t e n s i t i e s . 2 : 3 . 1 ( C a l c . 2 : 3 . 0 ) . ( d ) T r i m e t h y l a r s i n e - - T r i m e t h y l a r s i n e w a s r e c o v e r e d f r o m t h e 38 t h e r m a l d e c o m p o s i t i o n o f c a c o d y l . I t w a s p u r i f i e d b y t r a p - t o -t r a p d i s t i l l a t i o n a n d i d e n t i f i e d b y i t s i n f r a r e d s p e c t r u m a n d m o l e c u l a r w e i g h t o f 123 ( C a l c ; 1 2 0 ) . T h e *H n . m . r . s p e c t r u m s h o w e d o n l y o n e p e a k a t - 0 . 7 4 p.p.m. (2) R e a c t i o n w i t h H.F.A. ( a ) D i m e t h y l a r s i n e - - D i m e t h y l a r s i n e ( 2 . 9 g) a n d t h e k e t o n e ( 3 - 9 g) w e r e l e f t a t 20° f o r o n e d a y a l t h o u g h a v i g o r o u s e x o t h e r -m i c r e a c t i o n t o o k p l a c e i m m e d i a t e l y o n m i x i n g . D i m e t h y l a r s i n e ( 0 . 2 g) w h i c h w e n t t h r o u g h a - 7 8 ° t r a p w a s r e c o v e r e d . A f r a c t i o n ( 0 . 1 g) w h i c h w e n t t h r o u g h a - 2 3 ° t r a p a n d c o n d e n s e d i n a - 7 8 ° t r a p w a s i d e n t i f i e d a s 1 , 1 , 1 , 3 , 3 7 3 - h e x a f l u p r o p r o p a n - 2 - o l ( F o u n d : C, 2 1 . 4 ; H, 1 .3 ; F, 6 7 . 2 %', m o l . w t . , 172. C a l c . f o r C ^ H ^ O : C, 2 1 . 4 ; H, 1 .2; F, 6 7 . 9 %', m o l . w t . , 168) . I n f r a r e d s p e c t r u m ( v a p o u r ) : 3664 w, 2990 w, 1426 w, 138O s, 1273 v s , 1248 s , 1207 v s , 1112 v s , 892 m, 735 w, 685 m c m " 1 . T h e m a i n p r o d u c t ( 6 . 5 g) w h i c h w a s r e c o v e r e d f r o m a - 2 3 ° t r a p w a s i d e n t i f i e d a s 2 - d i m e t h y l a r s i n o h e x a f l u o r o p r o p a n - 2 - o l ( F o u n d : C, 2 2 . 1 ; H, 2 . 7 ; A s , 2 7 - 8 ; F, 4 2 . 1 %. C a l c . f o r C .H A s F , 0 : 5 7 ° C, 2 2 . 1 ; H, 2 . 6 ; A s , 2 7 . 6 ; F, 4 1 . 9 %) • I n f r a r e d s p e c t r u m ( v a p o u r ) : 3635 m, 3020 w, 2950 w, 1428 w, 1379 m, 1269 v s , 1228 m ( s h ) , 1205 v s , 1138 m, 1107 s , 943 m, 873 m, 851 m, 75.0 m, 708 m c m " 1 . N.m.r. s p e c t r a : t h e *H n . m . r . s p e c t r u m s h o w e d t w o p e a k s , o n e a t - 1 . 1 6 p.p.m. (-CH^) a n d t h e o t h e r a t - 3 - 5 2 p.p.m. (-OH). T h e C h e m i c a l s h i f t s r e l a t i v e t o b e n z e n e a n d w a t e r h a v e b e e n r e p o r t e d 10 a d d i t i o n o f a l a r g e e x c e s s o f H.F.A. s h i f t e d t h e p e a k s t o - 1 . 2 0 ]Q p.p.m. a n d -3-1+5 p.p.m. T h e ; F n.m . r . s p e c t r u m s h o w e d o n e p e a k a t - 6 . 6 3 p.p.m. A d d i t i o n o f e x c e s s H.F.A. d i d n o t p r o d u c e any-f u r t h e r p r o d u c t p e a k s . T h e f o l l o w i n g v a p o u r p r e s s u r e d a t a w e r e o b t a i n e d f o r t h e a r s i n e : o 1 3 ° -1 T K p cm l o g p j x 10 K 3 l U 2 . 2 8 0 . 3 5 7 3 . 1 9 335 6 . 9 U 0.81+1 2 . 9 9 3I+6 11.86 1.07)4. 2 . 8 9 351 1 5 . U l 1 .188 2 . 8 5 3 7 1 . 2 3 0 . 7 5 1.14-86 2 . 7 0 379-1 1+2.56 1.628 2 . 6 ' 388 5 6 . 3 2 1.7I4.2 2.5 3 9 5 . 6 71.51+ 1 .855 2 . 5 3 . A l i n e a r p l o t o f l o g p a g a i n s t y w a s o b t a i n e d t o g i v e a n e x t r a p -o l a t e d b o i l i n g p o i n t o f 12l+ ± 0 . 5 ° . ( b ) Me t h y 1 a r s i n e - - M e t h y l a r s i n e (1+.8 g) a n d H.F.A. ( 3 . 3 g) w e r e l e f t a t 20° f o r t h r e e h o u r s . M e t h y l a r s i n e ( 3 - 3 g) w h i c h ' w e n t t h r o u g h a - 7 8 t r a p w a s r e c o v e r e d . T h e r e a c t i o n p r o d u c t , h e x a -f l u o r o - 2 - m e t h y l a r s i n o p r o p a n - 2 - o l (1+.1+ g) , w a s r e c o v e r e d f r o m a - 7 8 ° t r a p ( F o u n d : C, 18.1+; H, 1 .8; A s , 2 8 . 9 ; F, L+1+.1+ %'» m o l . w t . , 2 5 1 . C a l c . f o r C. H AsF.O: C, 1 8 . 6 ; H, 1 .9; A s , 2 9 . 1 ; F, 1+1+. 1 %; 1+5 6 m o l . w t . , 2 5 8 . I n f r a r e d s p e c t r u m ( v a p o u r ) : 3620 w, 2955 w> 2925 vw, 211+5 m, 11+21+ w, 1377 w, 1277 v s , 1230 m ( s h ) , 1206 v s , 111+3 m, 1106 s , 953 m, 882 m, 8I+3 w, 71+1 m, 700 m c m " 1 . N.m.r. s p e c t r a : t h e *H n . m . r . s p e c t r u m s h o w e d t h r e e p e a k s , a s i n g l e t a t - 1 . 2 2 p.p.m. (-CH^) a n d - 3 . 6 2 p.p.m. (-OH) a n d a m u l t i p l e t a t - 3 . 6 p.p.m. ( A s - H ) ( J = 7.5 c p s ) . ( A s - C H ^ ) - ( A S - H ) T h e f o l l o w i n g v a p o u r p r e s s u r e d a t a w e r e o b t a i n e d f o r t h e m e t h y l a r s i n o p r o p a n o 1 : o I 3 0 - I T K p cm l o g p ^ x 1 0 J K 311+ 6.5 0 . 8 1 3 3-19 11 T ° K p cm l o g p A x 1 0 3 ° K~ 3 2 1 . 6 10.3 1.013 3.11 ' 331 16 .k 1.215 3 . 0 3 ' 3kh 2 8 . 4 5 l.kSk 2 .91 352 3 8 . 3 1 . 5 8 V 2 . 9 5 3 6 0 . 8 5 0 . 0 1.700 2,77 367 5 7 . 2 5 1.758 2 . 7 3 S l i g h t d e c o m p o s i t i o n o f t h e c o m p o u n d o c c u r r e d , c o n s e q u e n t l y t h e e x t r a p o l a t e d b o i l i n g p o i n t o f 117 - 2 ° i s n o t v e r y ; a c c u r a t e . I n a s e c o n d e x p e r i m e n t m e t h y l a r s i n e ( 3 - 5 9) a n d e x c e s s k e t o n e ( 1 6 . 9 g) w e r e l e f t a t 2 0 ° f o r o n e d a y . H.F.A. ( 6 . 2 g) w h i c h w e n t t h r o u g h a - 7 8 ° t r a p w a s r e c o v e r e d . T h e i n e t h y l a r s i n o p r o p a n o l (I4..7 9) o f k n o w n i n f r a r e d s p e c t r u m w a s p r o d u c e d . ( c ) M e t h y l a r s i n o h e x a f l u o r o p r o p a n - 2 - o 1 - - T h e a r s i n o p r o p a n o l (LL.1+ g) a n d H.F.A. ( 6 . 5 g) w e r e ' . l e f t a t 2 0 ° f o r 20 d a y s . H.F.A. (3-6 g) w a s r e c o v e r e d . A f r a c t i o n ( 0 . 5 g) w h i c h s t o p p e d i n a - 7 8 t r a p w a s i d e n t i f i e d a s 1, 1, 1,3 >3 , 3 - b . e x a f l u o r o p r o p a n o l b y i t s i n f r a r e d s p e c t r u m . A n i n v o l a t i l . e c o l o u r l e s s s o l i d ( 6 . 8 g) w h i c h w a s e x t r e m e l y a i r s e n s i t i v e a n d w h i c h w a s n o t i d e n t i f i e d w a s a l s o p r o d u c e d . ( d ) T r i m e t h y l a r s i n e - - l t w a s f o u n d t h a t m i x t u r e s o f t h e k e t o n e a n d t r i m e t h y l a r s i n e c o u l d n o t b e s e p a r a t e d b y t r a p - t o - t r a p d i s t i l - . l a t i o n . T h e m i x t u r e r e p e a t e d l y s t o p p e d i n a t r a p c o o l e d t o - 6 L L ° , t h u s s h o w i n g l o w e r ' v o l a t i 1 i t y t h a n e i t h e r c o m p o n e n t s e p a r a t e l y ( H . F . A . g o e s t h r o u g h a - 9 6 ° t r a p a n d t r i m e t h y l a r s i n e g o e s t h r o u g h a - 7 8 ° t r a p ) . N.m.r. s p e c t r a : A t 2 0 ° t h e *H n . m . r . s p e c t r u m o f t r i m e t h y l -a r s i n e s h o w e d o n e p e a k a t -O.7I+ p.p.m. A t 2 0 ° a s o l u t i o n o f t r i -m e t h y l a r s i n e i n e x c e s s H.F.A. g a v e o n l y a s i n g l e u n s p l i t p e a k a t —0.14.I4. p.p.m., a n d a t 2 0 ° t h e * ^ F n . m . r . s p e c t r u m a l s o s h o w e d o n l y o n e p e a k . A t 0 ° t h e same s o l u t i o n s h o w e d a b r o a d m e t h y l p e a k ( J s s 0 . 5 c p s ) . T h e s o l u t i o n s o l i d i f i e d b e t w e e n - 5 a n d - 1 0 ° . 12 ( e ) C h l o r o d i m e t h y l a r s i n e - - T h e c h l o r o a r s i n e ( 3 . 2 g) a n d H.F.A. ( 6 . 1 g) w e r e i m m i s c i b l e a t 20° a n d t e m p e r a t u r e s u p t o 1 0 0 ° . T h e r e a c t a n t s w e r e t h e n h e a t e d t o 1 2 0 ° ' f o r t h r e e h o u r s , 200° f o r 15, h o u r s a n d 250° f o r f i v e : h o u r s w i t h o u t r e s u l t . R e c o v e r y o f b o t h r e a c t a n t s w a s n e a r l y q u a n t i t a t i v e (3*1 g a n d 6 . 1 g ) . ( f ) T e t r a m e t h y l d i a r s i n e - - P r e 1 i m i n a r y s t u d i e s o n a m i x t u r e o f t h e d i a r s i n e a n d H.F.A... i n d i c a t e d t h a t t h e y r e a c t t o p r o d u c e a n o n v o l a t i l e l i q u i d w h i c h , i s u n s t a b l e t o a i r . T h e i n f r a r e d s p e c -t r u m o f a s o l u t i o n o f d i a r s i n e ( 0 . 6 5 g) a n d H.F.A. ( 0 . 2 g) s h o w e d t h e f o l l o w i n g a b s o r p t i o n b a n d s : 3 - 3 5 w, 3 - 4 5 w, 3-57 w, 5«5 vw, 5 . 8 7 vw, 7 - l m , 8 . 0 5 v s , 8 . 5 v s , 9 . 0 5 v s , 1 0 . 2 5 m, 1 0 . 6 5 m, 11.15 m, I I . 7 8 m, 12.13 m, 12 .63 vw, 13.36 w, 13.57 w, 13 .8 w, li|. 12 w/< . N.m.r., s p e c t r a : t h e H n . m . r . s p e c t r u m o f t h e d i a r s i n e c o n s i s t s o f o n e p e a k a t - 1 . 1 3 p.p.m. A m i x t u r e o f t h e d i a r s i n e a n d e x c e s s H.F.A. ( 2 : 7 b y v o l u m e ) r e s u l t s i n t w o p e a k s o f e q u a l a r e a a t - 0 . 7 1 p.p.m. a n d - 0 . 9 3 p.p.m. I n a 1:1 m o l a r m i x t u r e t h e t w o p e a k s a r e s h i f t e d d o w n f i e l d t o -1 .07 : p.p.m. a n d - 1 . 3 0 p.p.m.., t h e h i g h f i e l d p e a k b e i n g a m u l t i p l e t ( J # 0 . 8 , c p s ) . T h e n.m.r / s p e c t r u m o f t h e d i a r s i n e i n e x c e s s H.F.A. s h o w s t w o p e a k s , o n e a t - I . 3 6 p.p.m. ( e x c e s s H.F.A.) a n d a n o t h e r a t -7.9)4. p.p.m. (3) R e a c t i o n s o f t h e D i a r s i n e - H . F . A . A d d u c t ( a ) W i t h W a t e r - - T h e d i a r s i n e ( 3 . 1 g) a n d H.F.A. (9-7 g) w e r e l e f t a t 20° f o r a f e w h o u r s . T h e e x c e s s k e t o n e w a s r e m o v e d a n d w a t e r w a s a d d e d t o t h e r e m a i n i n g l i q u i d . T e t r a m e t h y l d i a r s i n e ( 3 . 0 g ) , o f k n o w n *H n . m . r . s p e c t r u m , w a s r e c o v e r e d f r o m a - 2 3 ° t r a p . ( b ) W i t h H e x a f 1 u o r o b u t - 2 - y n e - - T e t r a m e t h y I d i a r s i n e ( 2 . 8 g) a n d a A c h e m i c a l s h i f t o f -1 .11 p.p.m., r e l a t i v e t o i n t e r n a l t e t r a -m e t h y l s i l a n e , f o r a c h l o r o f o r m : s o l u t i o n h a s b e e n r e p o r ted^-O. 13 H.F.A. ('5.2 g) w e r e l e f t a t 20° f o r a f e w h o u r s . T h e e x c e s s k e t o n e ( 2 . 9 g) w a s r e c o v e r e d a n d h e x a f l u o r o b u t - 2 - y n e (13•7 g) w a s a d d e d t o t h e r e m a i n i n g 1:1 a d d u c t . : T h e v o l a t i l e s ( 1 3 - 0 g) w e r e r e c o v -e r e d a n d a d d e d t o w a t e r t o r e m o v e H.F.A. a s a h y d r a t e . H e x a f l u o r o -b u t - 2 - y n e ( 1 1 . 5 g) w h i c h w e n t t h r o u g h a ' - 7 8 ° t r a p w a s r e c o v e r e d . T h e i n v o l a t i l e r e a c t i o n p r o d u c t ( 5 . 1-9) w h i c h r e m a i n e d i n t h e r e a c -t i o n t u b e w a s i d e n t i f i e d a s a m i x t u r e o f c i s - a n d t r a n s - 2 , 3 - b i s -( d i m e t h y l a r s i'no) h e x a f l u o r o b u t - 2 - e h e , ' b . p . 9 1 ° ( 12 mm)' ( l i t . '99° h i 19 41 (17 mm)) , b y m e a n s o f i t s k n o w n i n f r a r e d a n d F n . m . r . s p e c t r a 19 T h e F n . m . r . ' s p e c t r u m c o n s i s t e d o f p e a k s a t - 2LL . 3 a n d - 2 6 . 3 p.p.m. o f r e l a t i v e i n t e n s i t i e s 10:1 ( c i s.: t r a n s ) . ( c ) W i t h H e x a f l u o r o b u t - 2 - y n e i n t h e P r e s e n c e o f E x c e s s H.F.A.." - - T e t r a m e t h y l d i a r s i n e ( 3 . 5 g) a n d H.F.A. (10 g) 'were l e f t a t 20° f o r t w o h o u r s a n d t h e n h e x a f l u o r b b u t - 2 - y n e ( 7 . 5 g)- w a s a d d e d . T h e r e a c t i o n p r o d u c t \ i s o l a t e d t w o d a y s l a t e r w a s i d e n t i f i e d a s a m i x t u r e o f c i s - a n d t r a n s - 2 , 3 ~ b i s ( d i m e t h y l a r s i n o ) h e x a f l u o r o b u t - 2 -e n e , b . p . 98° ( 15 mm) ( l i t . 9 9 ° ( 17 mm)) , w h i c h t h e ^ F n.m.r. s p , e c t r u m s h o w e d t o be 9 L $ c i s - i s o m e r . C. R e a c t i o n o f G r o u p I V H y d r i d e s w i t h H e x a f l u o r o a c e t o n e (1) S y n t h e s i s o f S t a r t i n g M a t e r i a l s T r i m e t h y l s i l a n e w a s p u r c h a s e d : f r o m P e n i n s u l a r : C h e m r e s e a r c h ' I n c . , G a i n s v i l l e ^ F l o r i d a ^ a n d .was u s e d w i t h o u t f u r t h e r p u r i f i - ; c a t i o n . I t s p u r i t y w a s c h e c k e d b y i t s i n f r a r e d s p e c t r u m a n d m o l -e c u l a r w e i g h t o f 7 4 . 7 ( C a l c : 7Lt. 1) . ( a ) T r i m e t h y l q e r m a h e - - T e t r a m e t h y l g e r m a n e w a s p r e p a r e d b y t h e r e a c t i o n o f m e t h y . l m a g n e s i u m i o d i d e a n d g e r m a n i u m t e t r a c h l o r i d e T e t r a m e t h y l g e r m a n e w a s s e a i e d i n a G a r i u s t u b e w i t h 0 . 0 5 m o l e e x -c e s s b r o m i n e a n d l e f t a t 20° f o r 8. day.s, t o g i v e t r i m e t h y l g e r m -43 ' a n i u m b r o m i d e . ; T h e g e r m a n i u m b r o m i d e w a s d i s s o l v e d i n 1M h y d r o b r o m i c a c i d a n d r e d u c e d b y s o d i u m b o r o h y d r i d e t o t r i m e t h y l -44 n o g e r m a n e . T r i m e t h y l g e r m a n e w h i c h w e n t t h r o u g h a -78 t r a p w a s p u r i f i e d b y t r a p - t o - t r a p d i s t i l l a t i o n . I t s p u r i t y w a s c h e c k e d b y i t s i n f r a r e d s p e c t r u m ( G e - H a t l | . 9 ^ ) a n d i t s . m o l e c u l a r w e i g h t o f 118 ( C a l c : 1 1 8 . 6 ) . ( b ) T r i m e t h y l t i n H y d r i d e a n d D i m e t h y l t i n D i h y d r i d e - - T r i m e t h -y l t i n c h l o r i d e w a s p r e p a r e d b y t h e d i r e c t a d d i t i o n o f s t a n n i c c h l o r i d e t o t e t r a m e t h y I t i n w i t h o u t t h e u s e o f a; s o l v e n t . D i -m e t h y l t i n d i c h l o r i d e ( p u r c h a s e d f r o m M & T C h e m i c a l s ) a n d t r i -m e t h y l t i n c h l o r i d e w e r e t h e n r e s p e c t i v e l y ' r e d u c e d b y l i t h i u m a l -45 -u m i n u m h y d r i d e i n n - b u t y l e t h e r T h e h y d r i d e s w e r e p u r i f i e d b y t r a p - 1 o - t r a p ' d i s t i 1 1 a t i o n . T h e p u r i t y o f t r i m e t h y l t i n h y d r i d e w a s c h e c k e d b y i t s i n f r a r e d s p e c t r u m a n d i t s m o l e c u l a r w e i g h t o f I63 ( C a l c : I6I4..7). D i b u t y l t i n d i h y d r i d e w a s s i m i l a r l y p r e p a r e d . (2) R e a c t i o n s w i t h H.F.A. ( a ) T r i m e t h y l s i l a n e - - T r i m e t h y 1 s i l a n e ( 2 . 2 g") a n d H.F.A. ( 9 - 0 g) w e r e h e a t e d a t 145° f o r 5 d a y s . H.F.A. ( 3 - 2 g) w h i c h w e n t t h r o u g h o a -96 t r a p w a s r e c o v e r e d . T h e m a i n f r a c t i o n ( 5 - 9 g) w h i c h w e n t o . o t h r o u g h a -23 t r a p a r i d c o n d e n s e d i n a -96 t r a p w a s i d e n t i f i e d a s 1 , 1 , 1 , 3 , 3 > 3 - h e x a f l u o r o p r o p o x y t r i m e t h y 1 s i l a n e , b . p . 86° (757 mm), , ( F o u n d : C, 2 9 . 7 ; H, 4 - 3 ; F> 4 7 - 2 %. C a l c . f o r C H F O S i : C, 3 0 . 0 ; 6 10 6 H, 4 - 2 ; F, 4 7 . 5 %) > I n f r a r e d s p e c t r u m ( v a p o u r ) : ' 3004 m, 2950 w, 1808 vw, 1589 vw, 1420 vw, 1378 s , 1307 v s , 1270 s , 1232 v s , 1212 v s , 1172 s , 1111 s , 1071 s , 879 s , 849 s , 758 m, 720 w, 685 m c m " 1 . N.m.r. s p e c t r a : t h e ' *H n . m . r . s p e c t r u m s h o w e d t w o p e a k s , o n e , a s i n g l e t . a t 0 . 1 6 p.p.m. (-CH ) a n d t h e o t h e r , a s e p t e t , , a t - 3 • 9 0 ^ 19 p.p.m. (-CH) ( J - 6 .0 c p s ) . T h e F "n.m.r. s p e c t r u m s h o w e d o n e p e a k , a d o u b l e t , a t - 0 . 6 5 p.p.m. ( J - 6 c p s ) . ' " Some l e s s v o l a t i l e m a t e r i a l ( 2 . 0 g) w a s a l s o i s o l a t e d f r o m a 15 o 1 - 2 3 t r a p . N.m.r. s p e c t r a : t h e H n . m . r . s p e c t r u m o f t h i s m a t e r -i a l s h o w e d m e t h y l a b s o r p t i o n s a t 0 . 0 2 a n d O . I L L p.p.m. a n d s e p t e t s a t - 3 - 9 5 a n d -LL.LL9 p.p.m. ( J = 6 . 0 c p s ) . I t w a s f o u n d t h a t t h i s s p e c t r u m , c o u l d be d u p l i c a t e d b y t h e a d d i t i o n o f H.F.A. t o e x c e s s 1> 1 > 1 } 3 , 3 , 3 - h e x a f l u o r o p r o p o x y t r i m e t h y 1 s i l a n e . U p o n a d d i t i o n o f 1 e x c e s s H.F.A. t h e H n.m . r . s p e c t r u m s h o w e d o n l y o n e m e t h y l a b -s o r p t i o n a t 0 . 0 8 p.p.m. a n d o n e d o w n f i e l d s e p t e t a t -LL.LL5 p.p.m. 19 ( J = 5 - 8 c p s ) a n d t h e F n.m.r. s p e c t r u m s h o w e d t h r e e p e a k s , t h e c e n t r a l o n e b e i n g d u e t o H.F.A. a n d t h e o t h e r t w o , o f e q u a l a r e a , b e i n g s i t u a t e d a t 5 -09 a n d - 2.£l p.p.m. f r o m i n t e r n a l H.F.A. O t h e r e x p e r i m e n t s w h i c h w e r e f o l l o w e d b y *H n.m.r. s p e c t r a i n d i c a t e d t h a t t r i m e t h y 1 s i l a n e a n d H.F.A. r e a c t s l o w l y b u t comp-l e t e l y (17 h o u r s ) a t 2 0 ° . ( b ) T r i m e t h y l g e r m a n e - - T h e g e r m a n e ( 6 . 3 5 g) a n d H.F.A. ( 2 . 3 g) w e r e l e f t a t 20° f o r 15 h o u r s . T r i m e t h y l g e r m a n e (LL . 8 0 g) w h i c h w e n t t h r o u g h a - 7 0 t r a p w a s r e c o v e r e d . T h e p r o d u c t , 1 , 1 , 1 , 3 , 3 , 3 -h e x a f l u o r o p r o p o x y t r i m e t h y l g e r m a n e ' (3 .81 g) , b . p . 1 1 7 ° (758 mm), c o n d e n s e d i n ,a - 7 8 ° t r a p ( F o u n d : C, 2 5 - 3 ; H, 3-6 %. C a l c . f o r C H F.GeO: C, 2 5 .LL; H, 3 . 7 %) . I n f r a r e d s p e c t r u m ( v a p o u r ) : 6 10 6 3015 w, 2920 w, 1LL18 W, I37I+ s, 130LL v s , 1275 s, 1217 v s , 1153 s , 1106 s, 894 m, 868 m, 827 s , 76O s , 685 m cm 1 . N.m.r. s p e c t r a : 1 . t h e H n. m . r . s p e c t r u m s h o w e d a s i n g l e t a t - 0 . 2 5 p.p.m. (-CH^) a n d a s e p t e t a t - 3 - 9 6 p.p.m. (-CH) ( J = 6 . 1 c p s ) , o f r e l a t i v e i n -19 t e n s i t y 1 : 8 . 9 ( C a l c : 1 : 9 . 0 ) . T h e F n.m.r. s p e c t r u m s h o w e d a d o u b l e t a t - 1 . 6 5 p.p.m. ( j # 6 c p s ) . A 2: 1 m o l a r p r o p o x y g e r m a n e -H.F.A. s o l u t i o n g a v e a *H n.m.r. s p e c t r u m w i t h m e t h y l p e a k s a t -0.1).3 a n d - 0 . 2 7 p.p.m. a n d a l s o s e p t e t s a t -LL . 7 4 a n d - 3 - 9 8 p.p.m. T h e *H n. m . r . s p e c t r u m o f t h e p r o p o x y g e r m a n e i n e x c e s s H.F.A. s h o w s o n l y o n e m e t h y l p e a k a t - 0 . 2 7 p.p.m. a n d o n e s e p t e t a t -LL . 5 6 16 19 p.p.m. ( J = 6 . 1 c p s ) . T h e F n.m . r . s p e c t r u m s h o w s t h r e e p e a k s , t h e c e n t r a l o n e b e i n g H . F . A . - a n d t h e o t h e r t w o , o f e q u a l i n t e n -s i t y , s i t u a t e d a t 3 - U- p.p.m. a n d - 2 . 9 p.p.m. f r o m i n t e r n a l H.F.A. T h e l o w f i e l d p e a k i s a m u l t i p l e t ( J = 6 a n d 2 . 5 c p s ) . ( c ) T r i m e t h y l t i n H y d r i d e - - T r i m e t h y 1 t i n h y d r i d e ( 5 - 0 g) a n d H.F.A. ( 3 . 6 g) r e a c t e d i m m e d i a t e l y o n m i x i n g . T r i m e t h y l t i n h y -d r i d e ( 1 . 2 g) w h i c h w e n t t h r o u g h a -1+6° t r a p w a s r e c o v e r e d . T h e r e a c t i o n p r o d u c t , 1 , 1 , 1 , 3 > 3 , 3 - h e x a f l u o r o p r o p o x y t r i m e t h y l t i n (7-3 g) J b . p . ; 7 6 ° (58 mm), c o n d e n s e d i n a -1+6° t r a p ( F o u n d : C, 2 1 . 3 ; H, 3 . 1 %; m o l . w t . ( b e n z e n e ) , 661+. C a l c . f o r C / H , _ F , O S n : b 10 o C, 2 1 . 8 ; H, 3«0 %', m o l . wt., 3 3 1 ) . I n f r a r e d s p e c t r u m ( v a p o u r ) : 3020 w, 2910 vw, 1371+ s, 1300 v s , 1275 s, 1210 v s , .1161+ s, 1101 s , 893 m, 859 m, 766 m, 71+6 m, 683 m cm . N.m.r. s p e c t r a : t h e *H n.m.r. s p e c t r u m s h o w e d a s i n g l e t a t -O . 3 8 p.p.m. (-CH^) a n d a 19 s e p t e t a t -1+.11+ p.p.m. (-CH) ( J = 6 . 1 c p s ) . T h e F n.m . r . s p e c -t r u m s h o w e d a d o u b l e t a t - 1 . 7 p.p.m. ( J ~ 6 c p s ) . . ( d ) H e x a f l u o r o p r o p o x y t r i m e t h y 1 1 i n - - T h e a d d i t i o n o f H.F.A. t o t h e p r o p o x y t i n c o m p o u n d g a v e a n e x o t h e r m i c r e a c t i o n . T h e e x c e s s H.F.A. w a s r e m o v e d b y p u m p i n g a n d t h e r e m a i n i n g m a t e r i a l w a s i d -o . e n t i f i e d a s a 1:1 p r o p o x y t i n - H . F . A . c o m p l e x , m.p. 23 ( F o u n d : C, 2 1 . 9 ; H, 2 . 2 ; F, 1+5-5; S n , 2 3 . 8 ^ . C a l c . f o r y ^ F ^ O ^ n : C, 2 1 . 7 ; H, 2 . 0 ; F, 1+6.0; S n , 2 3 . 9 %) • I n f r a r e d s p e c t r u m •( l i q u i d f i l m ) : 3005 w , 2 9 3 5 w, 1373 s, 1353 m, 1308 s, I 2 8 9 s, 1220 v s ( b ) , 1110 s, 1101 w ( s h ) , 970 s , 898 m, 882 w, 783 m, 71+7 w, 725 w, 718 m, 681+ m, 667 w cm N.m.r. s p e c t r a : t h e ^ H n . m . r . s p e c -t r u m o f t h e c o m p l e x i n H.F.A. s h o w s a s i n g l e t a t - 0 . 2 7 p.p.m. (-CH-j) a n d a s e p t e t a t -1+.58 p.p.m. (-CH) ( J = 6 . 1 c p s ) , o f r e l -19 a t i v e i n t e n s i t y 1 : 8 . 5 ( C a l c . 1 : 9 . 0 ) . T h e F n . m . r . s p e c t r u m s h o w s b r o a d p e a k s o f e q u a l i n t e n s i t y o f 1+.1+ a n d - 3 - 1 p.p.m; f r o m i n t e r n a l H.F.A. r e f e r e n c e . T h e *H n.m . r . s p e c t r u m o f a m i x t u r e 17 o f t h e c o m p l e x a n d t h e u n c o m p l e x e d s p e c i e s ( 1 , 1 , 1 , 3 , 3 > 3 - h e x a -f l u o r o p r o p o x y t r i m e t h y l t i n ) s h o w s o n l y o n e m e t h y l p e a k a t - 0 . 4 7 p.p.m. b u t t w o d o w n f i e . l d s e p t e t s , o n e a t -[4.. 13 p.p.m. a n d t h e 19 o t h e r a t - 4 - 8 4 p.p.m. T h e F n.m.r. s p e c t r u m o f t h e same m i x -t u r e s h o w s t h r e e p e a k s , a w e l l - d e f i n e d d o u b l e t a t - 1 . 4 5 p.p.m. a n d b r o a d p e a k s a t 2 . 9 a n d - 4 - 7 5 p.p.m. ' ( e ) D i m e t h y 1 t i n D i h y d r 1 d e - - D i m e t h y 11 i n ' ' d i h y d r i d e ( 1 . 6 4 g) a n d H.F.A. ( 4 - 4 3 g) r e a c t e d i m m e d i a t e l y o n m i x i n g . No v o l a t i l e s w e r e r e c o v e r e d . T h e p r o d u c t , b i s ( 1 , 1 , 1 , 3 , 3 > 3 - h e x a f l u o r o p r o p a n -o x y ) d i m e t h y I t i n , w a s p u r i f i e d b y d i s t i l l a t i o n , b . p . 9 2 ° (25 mm), ( F o u n d : C, 2 0 . 1 ; H, 1.7 %.' G a l e , f o r C g H g F ^ C ^ S n : C, 1 9 . 9 ; H, 1.7:%). I n f r a r e d s p e c t r u m ( l i q u i d f i l m ) : 2915 w, 1374 m, 1292 s, 1265 m, 1213 v s ( b ) , 1189 v s , 1145 m, IO98 s , 892 m, 855 m, 790 m, 747 m, 685 m cm 1 . N.m.r. s p e c t r a : t h e *H n. m . r . s p e c t r u m s h o w s a . s i n g l e t a t -O . 8 5 p.p.m. (-CH^) a n d a s e p t e t a t - 4 - 5 7 p.p.m. (-CH) ( J = 6 . 2 c p s ) o f r e l a t i v e i n t e n s i t y 1 : 3 . 0 5 ( C a l c . 1 : 3 . 0 ) . 19 T h e F n . m . r . s p e c t r u m . o f a 60% s o l u t i o n i f t c a r b o n t e t r a c h l o r i d e s h o w s a d o u b l e t a t - 2 . 0 7 p.p.m. ( J & 6 c p s ) . ( f ) B i s ( p r o p a n o x y ) d i m e t h y I t i n - - T h e b i s ( p r o p a n o x y ) d i m e t h y I t i n ( 0 . 4 0 4 4 g) a n d H.F.A. w e r e r e a c t e d a t 2 0 ° . T h e e x c e s s H.F.A. w a s r e m o v e d by p u m p i n g a n d a 1:2 c o m p l e x " ( 0 . 6 7 5 9 g) o f b i s ( p r o p a n o x y ) -d i m e t h y l - t i n - ' 2 H . F . A . r e s u l t e d ( F o u n d : C, 2 0 . 8 ; H, 1 .5; H.F.A., 4 0 . 2 %. C a l c . f o r c 1 j + H Q F 2 i 4 . ° h . S n : C ' 2 0 ' 6 ; H, 1 . 0 ; H.F.A., 4 0 . 7 %) • I n f r a r e d s p e c t r u m ( l i q u i d f i l m ) : v e r y s i m i l a r t o t h e u n c o m p l e x e d . s p e c i e s w i t h t h e a d d i t i o n o f t h r e e b a n d s : 970 s , 1024 w, 718 w cm R a p i d h y d r o l y s i s o f t h e c o m p o u n d c a u s e d b r o a d e n i n g i n C F s t r e t c h i n g r e g i o n m a k i n g i t d i f f i c u l t t o a s s i g n bands'. N.m.r. s p e c t r a : t h e *H n. m . r . s p e c t r u m s h o w s a s i n g l e t a t - 1 . 0 3 p.p.m. (-CHn) a n d a s e p t e t a t - 4 - 8 8 p.p.m. ( J = 6 . 0 c p s ) o f 18 19 r e l a t i v e i n t e n s i t y 1 : 2 . 9 . ( C a l c . 1 : 3 - 0 ) ' T h e F n . m . r . s h o w e d t w o b r o a d p e a k s o f e q u a l i n t e n s i t y a t 4 - 3 6 a n d - 2 . 9 4 p.p.m. w i t h r e s p e c t t o i n t e r n a l H.F.A. V a r i o u s m i x t u r e s o f t h e u n c o m p l e x e d s p e c i e s , b i s ( 1 , 1 , 1 , 3 , 3 > 3 _ h e x a f l u o r o p r o p o x y ) d i m e t h y 1 1 i n , a n d t h e 1 1:2 c o m p l e x s h o w e d t h r e e m e t h y l p e a k s i n t h e H n.m.r. s p e c t r u m . F o r e x a m p l e : a n a p p r o x i m a t e 1:1 m o l a r m i x t u r e o f t h e a b o v e - m e n -t i o n e d s p e c i e s s h o w e d p e a k s a t - 0 . . 8 0 , - 0 . 9 2 a n d - 1 . 0 5 p.p.m. o f r e l a t i v e i n t e n s i t i e s 2 : 5 - 2 r e s p e c t i v e l y . ( g ) D i b u t y I t i n D i h y d r i d e ^ - D i b u t y l t i n d i h y d r i d e ( 3 - 3 g) a n d H.F.A. ( '12.4 g) r e a c t e d i m m e d i a t e l y u p o n m i x i n g . H.F.A. ( 4 . 1 g) wa s r e c o v e r e d . T h e i n v o l a t i l e f r a c t i o n ( 1 1 . 5 g) w a s d i s t i l l e d a t -3 ^ 0 10 J mm a n d a t a p p r o x i m a t e l y • • 50 l o s s o f H.F.A.' o c c u r r e d . T h e H.F.A. w a s i d e n t i f i e d : b y i t s i n f r a r e d 1 s p e c t r u m a n d m o l e c u l a r w e i g h t o f 165 ( C a l c : 166). T h e m a i n f r a c t i o n w h i c h d i s t i l l e d a t 7 6 ° (10 ^ mm) w a s i d e n t i f i e d a s b i s ' ( 1, 1, 1 , 3 , 3 5 3 - h e x a f l u o r o p r o p -o x y ) d i b u t y l t i n ( F o u n d : C, 3 0 . 0 ; H, 3 . 6 ; S n , 2 1 . 6 ; F , 3 8 . 9 % . C a l c . f o r C ^ H ^ F ^ C ^ S n : C, 2 9 . 6 ; H, 3 - 5 ; " S n , 2 0 . 9 ; F, 4 0 . 2 %) . I n f r a r e d s p e c t r u m ( 1 i q u i d f i lm) : 2950 s, 2860 m, II4.67 m, H4.I7 w, 1372 s , 1284 v s , 1257 s, 1207 v s , 1185 v s , I I 3 1 s , 1092 v s , IO25 w, 958 w, 891 s , 855 s , 748 s , 684 s cm" 1.' B e f o r e d i s t i l -l a t i o n t h e r e w a s a s t r o n g b a n d a t 970 cm 1 . ( h ) T r i m e t h y l t i n C h l o r i d e - - A s o l u t i o n o f t r i m e t h y l t i n c h l o r i d e o a n d e x c e s s H.F.A. was' i m m i s c i b l e a t 20 . T h e r e a c t a n t s w e r e s t i l l i m m i s c i b l e a t 120° a n d h e a t i n g a t t h i s t e m p e r a t u r e f o r 12 h o u r s r e s u l t e d i n n o c h a n g e . (3) R e a c t i o n o f 1, 1 , 1 , 3 , 3 , ; 3 - H e x a f l u o r o p r o p o x y t r i m e t h y I t i n a n d 1, 1, 1 - T r i f l u o r o a c e t o n e  A n e x c e s s o f t h e p r o p o x y t i n i n t r i f l u o r o a c e t o n e s h o w e d o n l y t h r e e p e a k s i n t h e n . m . r . s p e c t r u m , t w o , a t - 0 . 2 7 a n d - 4 - 0 5 19 p.p.m., b e l o n g i n g t o t h e u n c h a n g e d p r o p o x y t i n a n d o n e , a t - 2 . 1 1 19 p.p.m., b e l o n g i n g t o t h e k e t o n e . T h e F n.m.r. s p e c t r u m o f t h e p r o p o x y t i n i n e x c e s s t r i f l u o r o a c e t o n e s h o w e d o n l y o n e p e a k , a w e l l - d e f i n e d d o u b l e t a t - 2 . 8 p.p.m. ( J £ 6 c p s ) f r o m i n t e r n a l t r i -f l u o r o a c e t o n e r e f e r e n c e . (1|) R e a c t i o n o f t h e 1:1 P r o p o x y t r i m e t h y l t i n - H . F .A. C o m p l e x a n d T r i m e t h y l t i n H y d r i d e . . 1 When e x c e s s 1:1 c o m p l e x w a s s e a l e d i n a H n.m.r. t u b e w i t h t r i m e t h y l t i n h y d r i d e t h e *H n . m . r . s p e c t r u m s h o w e d t h a t w i t h i n t w o m i n u t e s a f t e r m i x i n g a t 20° t h e r e a c t i o n w a s v i r t u a l l y c o m p -l e t e . T h e t r i m e t h y l t i n h y d r i d e p e a k s d i s a p p e a r e d a n d t h e s p e c t r u m s h o w e d t w o s e t s o f s e p t e t s i n d i c a t i n g t h e p r e s e n c e , o f u n c o m p l e x e d i 1 , 1 , 1 , 3 , 3 J 3 - h e x a f l u o r o p r o p o x y t r i m e t h y I t i n . 20 D I S C U S S I O N A. A r . s i n . e s ( 1) R e s u l t s H e x a f l u o r o a c e t o n e r e a c t s v i g o r o u s l y w i t h d i m e t h y l a r s i n e t o g i v e t h e e x p e c t e d a r s i n o p r o p a n o 1 , b . p . 12l+° ( 7 6 0 mm), i n g o o d y i e l d . ( C H ^ ^ s H + ( C F 3 ) 2 C O > ( C H 3 ) 2 A s C ( C F 3 ) 2 O H T h e s t r u c t u r e o f t h e p r o d u c t i s s h o w n b y t h e O-H i n f r a r e d a b s ' o r p -"I 1 t i o n a t 366I4. cm a n d b y i t s H n . m . r . s p e c t r u m o f o n l y t w o s h a r p p e a k s , t h e m e t h y l a b s o r p t i o n a t -1.16 p.p.m. a n d t h e OH a b s o r p -t i o n a t -3 - 5 2 p.p.m. M e t h y l a r s i n e a l s o r e a c t s v e r y r e a d i l y w i t h h e x a f l u o r o a c e t o n e . W i t h e x c e s s a r s i n e t h e p r o d u c t , i n h i g h y i e l d , i s h e x a f l u o r o - 2 -m e t h y l a r s i n o p r o p a n - 2 - o 1 , b . p . 1 1 7 ° ( 7 6 0 mm). R e d u c t i o n o f t h e k e t o n e t o 1 , 1 , 1 , 3 , 3 , 3 _ h e x a f l u o r o p r o p a n o l , a c o m p o u n d w h i c h h a s b e e n p r e p a r e d b y t h e r e d u c t i o n o f h e x a f l u o r o a c e t o n e b y l i t h i u m a l u m i n u m h y d r i d e ^ * a n d a G r i g n a r d r e a g e n t ^ ^ : ^ , a l s o o c c u r s t o a s m a l l e x t e n t {2.$%). C H 3 A s H 2 + ( C F ^ ) 2 C O > C H 3 A s H C ( C F 3 ) 2 O H + ( C F "JgCHOH T h e s t r u c t u r e o f t h e m a i n r e a c t i o n p r o d u c t ' i s ' s h o w n b y t h e 0-H a n d A s - H i n f r a r e d a b s o r p t i o n s a t 3 6 2 0 a n d 211+5 cm r e s p e c t i v e l y a n d b y i t s *H n . m . r . s p e c t r u m o f t h r e e p e a k s , t h e m e t h y l a b s o r p -t i o n a t - 1 . 2 2 p.p.m. a n d t h e 0-H a n d A s - H a b s o r p t i o n s o v e r l a p p i n g a t - 3 - 6 p.p.m. w i t h J , . = 7 - 5 c p s . T h i s o b s e r v e d v a l u e ( A s ) C H 3 - ( A s ) H o f t h e c o u p l i n g c o n s t a n t i s o f t h e same o r d e r o f m a g n i t u d e a s J , , f o r m e t h y l a r s i n e a n d d i m e t h y l a r s i n e . ( A s ) C H 3 - ( A s ) H . J y F u r t h e r r e a c t i o n o f t h e r e m a i n i n g A s - H b o n d w i t h h e x a f l u o r o -a c e t o n e i s m u c h s l o w e r s i n c e e v e n i n t h e p r e s e n c e o f e x c e s s k e t o n e 21 t h e 1:1 p r o d u c t c a n b e i s o l a t e d i n Lfl% y i e l d a f t e r o n e d a y a t 2 0 ° . N e v e r t h e l e s s t h e 1:1 a d d u c t e v e n t u a l l y r e a c t s c o m p l e t e l y w i t h t h e k e t o n e t o g i v e a n u n i d e n t i f i e d , u n s t a b l e , c o l o u r l e s s s o l i d w h i c h i s i n s o l u b l e i n t h e k e t o n e . A c o n s i d e r a b l e a m o u n t o f •1 J 1 , 1 > 3»3 J 3 - h e x a f l u o r o p r o p a n o 1 i s a l s o o b t a i n e d . A d a m s a n d P a l -m e r ^ ' ^ f o u n d t h a t p h e n y l a r s i n e r e a c t s w i t h a l d e h y d e s i n t h r e e d i f f e r e n t w a y s . A p p l y i n g t h e s e r e s u l t s t o t h e r e a c t i o n o f m e t h y l -a r s i n e a n d h e x a f l u o r o a c e t o n e t h e f o l l o w i n g e q u a t i o n s a r e o b t a i n e d . C H 3 A s H 2 + 2 ( C F ^ C O > C H ^ A s j C O H f C F ^ ^ . ( a ) ( 0 & 2 C H 3 A s H 2 * L L ( C F 3 ) 2 C O — > ^ ^ " ^ ^ + 2 ^ ) 2 C H O H ( b ) x C H A s H + x ( C F ) CO — — > ( C H A s ) + x ( C F ) CMOH ( c ) 3 2 3 2 3 x 3 2 E q u a t i o n ( c ) c a n be e l i m i n a t e d s i n c e ( C H y \ s ) x w h i c h i s a r e d s o l i d o r y e l l o w l i q u i d i s n o t f o r m e d . T h e . s t o c h i o m e t r y o f t h e r e a c t i o n o f t h e k e t o n e t o t h e m e t h y l a r s i n o p r o p a n o 1 i s 1:1', t h u s i t a p p e a r s p r o b a b l e t h a t s t e p w i s e a d d i t i o n o f h e x a f l u o r o a c e t o n e t o m e t h y l -a r s i n e o c c u r s t o g i v e t h e r e a c t i o n p r o d u c t f o r m e d i n e q u a t i o n ( a ) . P e r f l u o r o c y c l o b u t a n o n e a d d s t o p h o s p h i n e t o g i v e a 1:2 a d -29 d u c t w h i c h i s r e p o r t e d t o be a c r y s t a l l i n e m a t e r i a l . T h e y i e l d o f h e x a f l u o r o p r o p a n o l b a s e d o n e q u a t i o n ( b ) . i s 35^« T h u s , i t i s p o s s i b l e t h a t t h e p r o d u c t o f r e a c t i o n ( a ) d e c o m p o s e s s l o w l y a c -c o r d i n g t o thh f o l l o w i n g e q u a t i o n . O — H 2 C H 3 A s [ C O H ( C F 3 ) J | 2 _ > C A s ' \A s C W 3 + 2 ( C F 3 ) 2 C O H T h e r e i s some e x p e r i m e n t a l e v i d e n c e f o r t h i s p r o p o s e d d e c o m p -o s i t i o n s i n c e f o r m a t i o n o f t h e c r y s t a l l i n e s o l i d a n d h e x a f l u o r o -p r o p a n o l o c c u r s e v e n a f t e r c o m p l e t e r e m o v a l o f h e x a f l u o r o a c e t o n e . T h e s e c r y s t a l s o x i d i z e i m m e d i a t e l y i n a i r . 2 2 T r i m e t h y l a r s i n e f o r m s a n a d d u c t w i t h h e x a f l u o r o a c e t o n e w h i c h s o l i d i f i e s a t a p p r o x i m a t e l y - 5 ° b u t a p p e a r s t o be c o m p l e t e l y d i s -s o c i a t e d a t 2 0 ° e v e n u n d e r h i g h a c e t o n e p r e s s u r e s . T h e l H n.m.r. s p e c t r u m o f a t r i m e t h y l a r s i n e - k e t o n e s o l u t i o n h a s a s h a r p m e t h y l o 0 a b s o r p t i o n a t 20 ; h o w e v e r a t 0 t h e m e t h y l p e a k i s b r o a d a n d c a n be r e s o l v e d a s a m u l t i p l e t w i t h c p s . ( C H 3 ) 3 A s + ( C F K m ^ Q°-» ( m j A s ' f r F ) ^ r n C h l o r o d i m e t h y l a r s i n e d o e s n o t f o r m s u c h a n a d d u c t w i t h h e x a f l u o r o -a c e t o n e . a n d i s i m m i s c i b l e w i t h t h e k e t o n e a t 1 0 0 ° . H e x a f l u o r o a c e t o n e a n d t e t r a m e t h y l d i a r s i n e . r e a c t t o g i v e a c o m p o u n d i n w h i c h t h e r e a r e t w o s e t s o f i n e q u i v a l e n t m e t h y l g r o u p s a n d i n w h i c h t h e t r i f l u o r o m e t h y 1 group's a r e e q u i v a l e n t a s s h o w n b y n . m . r . s p e c t r o s c o p y . T h e c h e m i c a l s h i f t s i n h e x a f l u o r o a c e t o n e a r e m a r k e d l y d e p e n d e n t o n c o n c e n t r a t i o n . C o n t i n u a l p u m p i n g o n a h e x a f l u o r o a c e t o n e - d i a r s i n e s o l u t i o n r e s u l t s i n t h e g r a d u a l l o s s o f t h e k e t o n e a n d t h e a p p e a r a n c e o f t h e u n c o m p l e x e d d i a r s i n e . 1 T h i s i s r e a d i l y s h o w n i n t h e H n . m . r . s p e c t r u m o f s u c h a s o l u -t i o n w h i c h s h o w s t h e s i n g l e d i a r s i n e p e a k a s w e l l a s t h o s e a s s i g n e d 1 t o t h e c o m p l e x . T h i s H n . m . r . s p e c t r u m c a n be d u p l i c a t e d w i t h a k e t o n e - d i a r s i n e s o l u t i o n c o n t a i n i n g e x c e s s d i a r s i n e ( s u c h a s o l u -t i o n a l s o s h d w s n o c a r b o n y l a b s o r p t i o n i n t h e i n f r a r e d s p e c t r u m ) . T h e s e r e s u l t s i n d i c a t e t h a t t h e c o m p o u n d d i s s o c i a t e s t o some e x -t e n t a t 2 0 ° . ( C H 3 ) 2 A s A s ( C H 3 ) 2 + ( C F 3 ) 2 C O ( C H 3 ) h _ A s 2 - ( C F 3 ) 2 C O T h e a d d i t i o n o f w a t e r , t o t h e 1:1 a d d u c t g i v e s q u a n t i t a t i v e r e c o v -e r y o f t h e d i a r s i n e . ( C H ^ ) ^ A s 2 - ( C F 3 ) 2 C O + x H 2 0 > ( C H 3 ) ^ A s 2 + ( C F ^ ) 2 C O x H 2 0 W h e r e a s h e x a f l u o r o b u t - 2 - y n e r e a c t s w i t h t h e d i a r s i n e t o g i v e a n 41 a p p r o x i m a t e 1:1 m i x t u r e o f t h e c i s - a n d t r a n s - b u t e n e , h e x a -23 f l u o r o b u t - 2 - y n e r e a c t s w i t h t h e 1:1 a d d u c t t o g i v e 90% c i s - i s o m e r . ( C H 3 ) ^ A s 2 - ( C F 3 ) 2 C O + C F ^ C s C C F ^ > ( C H 3 ) 2 A s C G F 3 = C G F 3 A s ( C H 3 ) 2 + ( C F ^ ) 2 C O T h e i n f r a r e d s p e c t r u m o f t h i s r e a c t i o n p r o d u c t i s a l m o s t i d e n t i c a l w i t h t h e p r e v i o u s l y d e s c r i b e d 2 , 3 - d i m e t h y l a r s i n o h e x a f l u o r o b u t - 2 -e n e e x c e p t t h a t t h e d o u b l e b o n d a b s o r p t i o n a t 6 . 3 / 1 i s . m u c h 19 s t r o n g e r i n d i c a t i n g a p r e d o m i n a n c e o f t h e c i s - i s o m e r . T h e F peak n.m.r. s p e c t r u m s h o w s t h a t t h e -2b..3 p . p . m . ^ i s v e r y m u c h e n h a n c e d a n d t h e r e f o r e t h i s p e a k i s a s s i g n e d t o t h e c i s - i s o m e r . T h e i s o m e r d i s t r i b u t i o n a s d e t e r m i n e d b y t h e r e l a t i v e i n t e n s i t i e s o f t h e 1 9 p e a k s i n t h e F n . m . r . s p e c t r u m i s a p p r o x i m a t e l y 90%> c i s - i s o m e r . When t h e b u t y n e . i s r e a c t e d w i t h t h e 1:1 a d d u c t i n t h e p r e s e n c e o f e x c e s s h e x a f l u o r o a c e t o n e t h e r e a c t i o n i s e v e n m o r e s t e r e o s p e c i f i c r e s u l t i n g i n a p r o d u c t w h i c h i s 9h% c i s - i s o m e r . (2) P r o p o s e d M e c h a n i s m s a n d S t r u c t u r e s T h e a d d i t i o n o f h e x a f l u o r b a c e t o n e t o p r i m a r y ^and s e c o n d a r y a r s i n e s i s a n a l o g o u s t o t h e r e a c t i o n o f p o l y f l u o r o k e t o n e s w i t h 2LL 2 ^ 2 9 s e c o n d a r y a m i n e s ^' ^ a n d p h o s p h i n e . T h e f o r m a t i o n o f t h e 0-H b o n d c a n b e e x p l a i n e d o n t h e b a s i s o f n u c l e o p h i l i c a t t a c k b y t h e a r s e n i c l o n e p a i r o n t h e c a r b o n y i c a r b o n o f t h e h e x a f l u o r o a c e t o n e t o f o r m a f o u r c o o r d i n a t e d i n t e r m e d i a t e R 2 A s C ( 0 " ) ( C F - ) H f o l l o w e d b y A s - H c l e a v a g e t o f o r m a n OH b o n d b y e i t h e r a n i n t e r -o r i n t r a m o l e c u l a r m e c h a n i s m . T h u s t h e s l o w r e a c t i o n a t 20° b e t -w e e n h e x a f l u o r o a c e t o n e a n d 1, 1, 1 , 3 > 3 > 3 - h e x a f l u o r o m e t h y l a r s i n o -p r o p a n o l c a n b e e x p l a i n e d o n t h e b a s i s o f a d e c r e a s e i n t h e a v -a i l a b i l i t y o f t h e a r s e n i c l o n e p a i r d u e t o t h e e l e c t r o n e g a t i v e , g r o u p - C ( C F 3 ) 2 O H . T h e i n e r t n e s s o f c h l o r o d i m e t h y l a r s i n e t o w a r d s 21+ h e x a f l u o r o a c e t o n e , h o w e v e r , m u s t be p a r t i a l l y d u e t o t h e A s - C l b o n d s t r e n g t h s i n c e t h e d i f f e r e n c e i n t h e f i r s t i o n i z a t i o n p o t -e n t i a l s o f m e t h y l a r s i n e ( 9 - 7 . e.v.) ( w h i c h r e a c t s r a p i d l y w i t h h e x a f l u o r o a c e t o n e ) a n d c h l o r o d i m e t h y l a r s i n e ( 9 - 9 e . v . ) i s o n l y 1+9 0.2 e . v K ' O n t h e b a s i s o f t h e t h e o r y t h a t n u c l e o p h i l i c a t t a c k b y t h e a r s e n i c l o n e p a i r o c c u r s o n t h e c a r b o n y l c a r b o n , i t i s p r o p o s e d t h a t t h e t r i m e t h y l a r s i n e - h e x a f l u o r o a c e t o n e c o m p l e x h a s t h e s t r u c -t u r e ( C H ^ ) y f s C t C F ^ ) ^ O . T h i s w o u l d e x p l a i n t h e v e r y s m a l l l i q u i d r a n g e ( i t a p p e a r s t h a t t h e c o m p l e x may b e a l m o s t c o m p l e t e l y d i s -s o c i a t e d o n m e l t i n g ) s i n c e i t a p p e a r s r e a s o n a b l e t o a s s u m e t h a t t h i s m o n o m e r . w o u I d be s u s c e p t i b l e t o d i m e r i z a t i o n , t r i m e r i z a t i o n , . x ( C H 3 ) 3 A S C ( C F 3 ) 2 o — ( c H 3 ] 3 A s / A s ( c H 3 ) 3 + - C ( C F _ ) o 0 — ^ A s C ( C F j o 0 — ^ A s C ( C F - ) o 0 — ^ A s C ( C F 0 ) o 0 — W s - e t c . 3 d j j d | 3 d | 3 d | ( C H 3 ) 3 ( C H 3 ) 3 ( C H 3 ) 3 ( C H 3 ) 3 T h e s i m i l a r i t y b e t w e e n t h e d i m e r a n d t h e p r o p o s e d p r o d u c t f r o m m e t h y l a r s i n e - h e x a f l u o r o a c e t o n e r e a c t i o n ( e q u a t i o n ( b ) ) i s t o be " n o t e d . T o a c c o u n t f o r t h e a l m o s t s t e r e o s p e c i f i c r e a c t i o n o f t h e d i a r s i n e - h e x a f l u o r o a c e t o n e a d d u c t w i t h h e x a f l u o r o b u t - 2 - y n e , t h e l i b e r a t i o n o f t h e d i a r s i n e w h e n t r e a t e d w i t h w a t e r , t h e a b s e n c e o f a n y c a r b o n y l s t r e t c h i n g f r e q u e n c y i n t h e i n f r a r e d s p e c t r u m , a n d t h e n . m . r . s p e c t r a , t h e f o l l o w i n g s t r u c t u r e a p p e a r s m o s t p r o b -a b l e f o r t h e c o m p l e x , ( C H ) 2 A s A s ( C H ) 2 • ( C F ) 2 C O : (^3)2 C 0 25 I n t h i s s t r u c t u r e o r i e a r s e n i c a t o m i s a c t i n g a s a d o n o r b e i n g f o u r c o o r d i n a t e d , a n d t h e o t h e r a s a n a c c e p t o r b e i n g f i v e - c o o r d i n a t e d i f t h e l o n e p a i r i s t h o u g h t o f o c c u p y i n g o n e s i t e . T r i v a l e n t a r s e n i c d o e s a c t a s a n e l e c t r o n a c c e p t o r i n t h e s p e c i e s A s C l , a n d - 50 A s F ^ a n d s i n c e t h e p o s i t i v e c h a r g e o n t h e a r s e n i c a t o m w i l l p r o m o t e d e l o c a l i z a t i o n o f t h e l o n e p a i r o n t h e a d j a c e n t a r s e n i c a t o m , i t i s p r o b a b l e t h a t t h e n e g a t i v e c h a r g e o n t h e o x y g e n w i l l b e s t a b i l i z e d b y d o n a t i o n t o t h e a r s e n i c a t o m . I n t h e e x t r e m e c a s e o f c o m p l e t e d e l o c a l i z a t i o n o f c h a r g e t h e p r o p o s e d s t r u c t u r e c a n b e t h o u g h t a s h a v i n g a n a r s e n i c - a r s e n i c d o u b l e b o n d . ( C F 3 ) a c — o . (cH 3) aAs=7k(CH 3) 2 I t a p p e a r s t h a t t h e f o r m e r p r o p o s e d s t r u c t u r e a t l e a s t p r e s e n t s a f a i r l y s i g n i f i c a n t c o n t r i b u t i o n t o . t h e m o l e c u l a r o r b i t a l s s i n c e t h e c h e m i c a l s h i f t o f t h e m e t h y l p r o t o n s i s v-ery s e n s i t i v e t o t h e p r e s e n c e o f h e x a f l u o r o a c e t o n e . T h e p r e s e n c e o f a n y l o c a l i z e d c h a r g e i n t h e c o m p l e x w o u l d t h e r m o d y n a m i c a 1 l y f a v o u r e x t e n s i v e s o l v o l y s i s b y a p o l a r s o l v e n t . B. G r o u p I V H y d r i d e s ( 1 ) R e s u l t s T h e a d d i t i o n o f h e x a f l u o r o a c e t o n e t o G r o u p I V h y d r i d e s t o g i v e 1 , 1 , 1 , 3 » 3 , 3 - h e x a f l u o r o p r o p o x y d e r i v a t i v e s c a n b e r e p r e s e n t e d b y t h e f o l l o w i n g e q u a t i o n s (M = S i , G e , S n ; R = C r L , n-C, H Q ) 3 4 7 ( C H 3 ) 3 M H + ( C F 3 ) 2 C O > ( C H 3 ) 3 M O C H ( C F 3 ) 2 R 2 S n H 2 + 2 ( C F 3 ) 2 C O » R g S n J o C r U C F ^ ) ^ 2 T h e r e a c t i o n s w i t h t h e t i n h y d r i d e s a r e v i g o r o u s a n d e x o t h e r m i c b u t a d d i t i o n t o t h e s i l a n e a n d g e r m a n e i s m u c h s l o w e r . A l l r e a c -t i o n s a r e q u a n t i t a t i v e . -26 T r i m e t h y l s i l a n e r e a c t s w i t h h e x a f l u o r o a c e t o n e a t 20° t o g i v e 1 >.1 >1»3 J 3 > 3 - h e x a f l u o r o p r o p o x y t r i m e t h y I s i l a n e , b . p . 86° (757 mm). I t i s i d e n t i f i e d b y i t s i n f r a r e d s p e c t r u m w h i c h s h o w s n o a b s o r p -t i o n i n t h e OH r e g i o n a n d a m e d i u m t o s t r o n g a b s o r p t i o n a t 1070 cm 1 a t t r i b u t e d t o t h e S i - O - C a s y m m e t r i c s t r e t c h i n g v i b r a t i o n , a n d b y i t s n . m . r . s p e c t r a . T h e *H n . m . r . s p e c t r u m s h o w s t h e m e t h -19 i n e a b s o r p t i o n a s a s e p t e t ( J = 6 . 0 c p s ) a n d t h e F n . m . r . s p e c -t r u m s h o w s t h e t r i f l u o r o m e t h y 1 a b s o r p t i o n a s a d o u b l e t ( J # 6 c p s ) . 29 51 A l t h o u g h s i l a n e s a r e k n o w n t o r e a c t w i t h k e t o n e s u p o n h e a t i n g ' 52 a n d u p o n u l t r a v i o l e t i r r a d i a t i o n t o g i v e a d d i t i o n p r o d u c t s , f o r e x a m p l e 270° ( C ^ H ^ S i H +• ( C 6 H ^ ) 2 C O > ( C 6 H ^ ) 3 S i O C H ( C 6 H ^ ) 2 C l ^ S i H + ( C H 3 ) 2 C O k i c i 3 S i O C H ( C H 3 ) 2 ( n - C l + H 9 ) 2 S i H 2 + 2 C F 2 C F 2 C F 2 C O U 2 ° > ( n-C^Hg) 2 S i(cOHCF C F ^ F ^ t h e a d d i t i o n o f h e x a f l u o r o a c e t o n e t o t r i m e t h y l s i l a n e i s t h e f i r s t r e p o r t e d e x a m p l e o f a n u n c a t a l y z e d a d d i t o n a t 2 0 ° . T h e r e a c t i o n o f h e x a f 1 u o r o a c e t o n e w i t h e x c e s s t r i m e t h y l g e r -o mane a t 20 r e s u l t s i n t h e q u a n t i t a t i v e p r e p a r a t i o n o f 1 , 1 , 1 , 3 » 3 » 3 ~ h e x a f l u o r o p r o p o x y t r i m e t h y l g e r m a n e , b . p . 1 1 7 ° (758 mm). ( C H ) G e H + ( C F ) CO * ( C H ) G e O C H ( C F ) 3 3 3 2 '3 3 3 2 A s i n t h e s i l a n e r e a c t i o n a l l t h e s p e c t r o s c o p i c e v i d e n c e c l e a r l y 1 i n d i c a t e s t h e f o r m a t i o n o f a G e - 0 b o n d . T h e H n . m . r . s p e c t r u m o f t h e p r o d u c t s h o w s t h e m e t h i n e a b s o r p t i o n a s a s e p t e t ( J = 6 . 1 c p s ) a n d t h e m e t h y l a b s o r p t i o n a s a s i n g l e t ( r e l a t i v e i n t e n s i t y 19 1 : 8 . 9 ) . I t s F n.m.r. s p e c t r u m s h o w s t h e t r i f l u o r o m e t h y 1 a b s o r p -t i o n a s a d o u b l e t ( J s ; 6 c p s ) . T h e i n f r a r e d a b s o r p t i o n s w h i c h c a n p r o b a b l y b e a s s i g n e d t o t h e C F s t r e t c h i n g a n d C F ^ d e f o r m a t i o n f r e q u e n c i e s o f t h e g e r m a n e , a n d t h e o t h e r h e x a f l u o r o p r o p o x y d e r -i v a t i v e s p r e p a r e d i n t h i s i n v e s t i g a t i o n , a r e g i v e n i n T a b l e I w h e r e 27 t h e y a r e c o m p a r e d w i t h t h e c o r r e s p o n d i n g b a n d s o f 1,1,1,3>3>3-h e x a f l u o r o p r o p a n o l . T h e s i m i l a r i t y o f t h e s p e c t r a i s a p p a r e n t . A d d i t i o n o f h e x a f l u o r o a c e t o n e t o e x c e s s t r i m e t h y l t i n h y d r i d e t o f o r m 1 , 1 , 1 , 3 , 3 , 3 - h e x a f l u o r o p r o p o x y t r i m e t h y l t i n , b . p . 76° (58 mm), o c c u r s q u a n t i t a t i v e l y b e l o w r o o m t e m p e r a t u r e a n d i s e x t r e m e l y v i g -o r o u s a n d e x o t h e r m i c . ( C H ^ S n H + ( C F ^ C O > ( C H 3 ) ^ S nOCH ( C F 3 ) 2 T h e i n f r a r e d a n d n.m.r. s p e c t r a c l e a r l y i n d i c a t e t h a t a CH'.bond a n d n o t a n OH b o n d i s f o r m e d . I t s *H n . m . r . s p e c t r u m s h o w s t h e 19 m e t h i n e a b s o r p t i o n a s a s e p t e t ( J = 6.1 c p s ) a n d t h e F n . m . r . ' s p e c t r u m s h o w s t h e t r i f l u o r o m e t h y l a b s o r p t i o n a s a d o u b l e t ( J ? s : 6 53 c p s ) . K u i v i l a f o u n d t h a t t i n l h y d r i d e s u s u a l l y r e d u c e k e t o n e s t o a l c o h o l s , b e i n g t h e m s e l v e s c o n v e r t e d t o d i t i n c o m p o u n d s . I n t h e p r e s e n t i n v e s t i g a t i o n s e v e n t h e p r e s e n c e o f e x c e s s t i n h y -d r i d e g i v e s n o t r a c e o f t h e r e d u c t i o n p r o d u c t 1 , 1 , l , 3 , 3 j 3 - h e x a -f l u o r o p r o p a n o l , C F ^ C H t O H j C F ^ . T A B L E I I N F R A R E D S P E C T R A OF 1, 1, 1,3,3, 3-HEXAFLUOROPROPOXY D E R I V A T I V E S 3 , H O C H ( C F 3 ) 2 M e 3 S i O C H ( C F 3 ) 2 M e ^ G e O C r K C F ^ ) 2 M e ^ S n O C H t C F ^ ) 2 A s s i g n m e n t 1380 s 1378 s 137U s 1374 s C F 1308 s 1307 v s 130LL v s 1300 v s 1273 v s 1270 s 1275 s 1275 s . 1207 v s 1232 • 1217 v s b 1210 v s D 1212 1172 s 1153 s 116LL S 1112 v s 1 1 1 1 s 1106 s 1101 s s t r e t c h i n g it u 685 m 685 m 685 m 683 m CF3 a _ j d e f o r m a t i o n V a p o u r s t a t e , v a l u e s i n cm D B r o a d I n a s i m i l a r m a n n e r r e a c t i o n o f h e x a f l u o r o a c e t o n e a n d d i -a l k y l t i n d i h y d r i d e s ( d i m e t h y l a n d d i - n - b u t y l ) a t 20° r e s u l t s i n t h e a d d i t i o n o f t w o m o l e s o f k e t o n e t o g i v e b i s ( 1 , 1 , 1 , 3 , 3 > 3 " h e x a -f l u o r o p r o p o x y ) d i m e t h y l t i n , b . p . 92° (25 mm), a n d b i s ( 1 , 1 , 1 , 3 , 3 » 3 -28 h e x a f l u o r o p r o p o x y ) d i - n - b u t y I t i n , b . p . 75 ( 10 mm). T h e b i s -( h e x a f l u o r o p r o p o x y ) d i m e t h y I t i n i s r e a d i l y c h a r a c t e r i z e d b y i t s *H n.m.r. s p e c t r u m o f a s e p t e t a t -1+.57 p.p.m. ( J = 6 . 2 c p s ) a n d 19 a s i n g l e t a t - 0 . 8 5 p.p.m. ( r e l a t i v e i n t e n s i t y 1 : 3 . 0 5 ) . I t s F n.m.r. s p e c t r u m s h o w s o n l y t h e e x p e c t e d d o u b l e t (J?s*6 c p s ) . T h e d i - n - b u t y l d e r i v a t i v e h a s a n ; - i n f r a r e d s p e c t r u m w h i c h i s a l m o s t i d e n t i c a l w i t h t h a t o f /the d i m e t h y l d e r i v a t i v e . I t w a s f u r t h e r f o u n d t h a t t h e h e . x a f l u o r o p r o p o x y d e r i v a t i v e s w i l l c o m p l e x w i t h h e x a f l u o r o a c e t o n e . T h u s h e x a f l u o r o p r o p o x y t r i -m e t h y l t i n a n d h e x a f l u o r o a c e t o n e f o r m a s t a b l e 1:1 c o m p l e x , m.p. 2 3 ° . ( C H 3 ) 3 S n O C H ( C F 3 ) 2 + ( C F ^ C O > (C H ^ ) 3 S n O C H ( C F 3 ) 2 « ( C F ^ ) 2 C O I t s *H n. m . r . s p e c t r u m s h o w s t h e m e t h i n e a b s o r p t i o n a s a s e p t e t ( J = 6 . 1 c p s ) a n d t h e m e t h y l a b s o r p t i o n a s a s i n g l e t ( r e l a t i v e 19 i n t e n s i t y 1 : 8 . 5 ) . I t s F n.m.r* s p e c t r u m g i v e s b r o a d a b s o r p t i o n s a t - 3 - 1 p.p.m. a n d I4..I4. p.p.m. ( f r o m i n t e r n a l h e x a f l u o r o a c e t o n e ) o f r e l a t i v e i n t e n s i t y 1:1 i n d i c a t i n g t w o d i f f e r e n t t y p e s o f t r i f l u o r o -m e t h y l g r o u p s , t h e h e x a f l u o r o p r o p o x y g r o u p i s a t - 3 . 1 p.p.m. a n d 1 1 1 t h e c o m p l e x e d h e x a f l u o r o a c e t o n e i s a t i+.u, p.p.m. T h e H n.m.r. s p e c t r u m o f a m i x t u r e o f t h e c o m p l e x e d a n d u n c o m p l e x e d p r o p o x y t i n c o m p o u n d s h o w s t w o d i s t i n c t s e p t e t s ( O . 6 9 p.p.m. d i f f e r e n c e ) b u t o n l y o n e m e t h y l a b s o r p t i o n . T h e *H a n d *^F n.m . r . d a t a ( c h e m i c a l s h i f t s a n d c o u p l i n g c o n s t a n t s ) o f t h e c o m p l e x e d a n d u n c o m p l e x e d h e x a f l u o r o p r o p o x y d e r i v a t i v e s a r e l i s t e d i n T a b l e I I . T A B L E I I . SOME lH AND 1 9 F C H E M I C A L S H I F T S . A N D C O U P L I N G C O N S T A N T S 3 C o m p o u n d & C H ^ £ > H b , C J H _ p d fopropoxy)6 ^ ° 2 e t o n e ) d p.pim. ppjm. c p s p.pjn. p.pjn. +0.16 - 3 - 9 0 6 . 0 - 0 . 6 5 f M e 3 S i O C H ( C F 3 ) 2 29 C o m p o u n d & C H 3 b 6H^C W & F ( p r o p o x y ) e S (comp l e x e d ^ k e t o n e ) ppjn* PPJTI. c p s p.pjTl. p.pjn. M e 3 S I O C H ( C F 3 ) 2 * ( C F ^ C O 9 +0.08 5.8 - 2 * 5 i n +5.09H M e 3 G e O C H ' ( C F 3 ) 2 -0.25 -3.96 6.1 -i.65 F -M e 3 G e O G H ( C F ' ) 2 ' ( C F ) 2 C O -0.27 -4-56 6.1 -2.9 h i + 3 . 4 h M e 3 S n O C H ( C F 3 ) 2 -O.38 -h.i-k 6.1 -1.7 f M e 3 S n O C H ( C F 3 ) 2 - ( C F ^ ) 2 C O -0.27 -4.58 6.1 - 3 - 1 h M e 2 S n ^ C H ( C F 3 ) ^ j 2 -0.85 -4.57 6.2 • . - 2 . 0 7 f J -2.-94* M e 2 S n p C H ( C F 3 ) X •• 2"(CF 3) 2 C O -1.03 -4.88 6.0 cl S p e c t r a r u n o n n e a t l i q u i d s u n l e s s o t h e r w i s e i n d i c a t e d . N e g -, a t i v e v a l u e s o f 9 a r e d o w n f i e l d . W i t h r e s p e c t t o e x t e r n a l t e t r a m e t h y 1 s i l a n e . ^ S e p t e t . : F r o m *H s p e c t r a . z D o u b l e t s f o r u n c o m p l e x e d p r o p o x y d e r i v a t i v e s j J ?s6 c p s . W i t h r e s p e c t t o e x t e r n a 1 t r i f l u o r o a c e t i c a c i d . 9 S o l u t i o n i n h e x a f l u o r o a c e t o n e . . W i t h r e s p e c t t o i n t e r n a l h e x a f l u o r o a c e t o n e . . \ D o u b l e t , J = 6 c p s , s p l i t i n t o s e p t e t , J = 2.5 c p s . ^ S o l u t i o n i n C C 1 , . 4 T h e h e x a f l u o r o p r o p o x y r s i l a n e a n d - g e r m a n e f o r m e a s i l y d i s s o c i a t e d o 1:1 c o m p l e x e s w i t h h e x a f l u o r o a c e t o n e a t 2 0 . ( C H j _ M O C H ( C F - ) _ + ( C F ) CO x = = ^ ( C H ) MOCH ( C F ) • ( C F x ) o C 0 3 3 3 2 3 2 3 3 3 2 3 2 M = S i , Ge T h e f o r m a t i o n o f t h e s e 1:1 c o m p l e x e s i s r e a d i l y s h o w n b y *H n.m.r. 19 1 a n d 7 F n . m . r . s p e c t r a . T h e H n . m . r . s p e c t r u m o f a 2:1 m o l a r h e x a f l u o r o p r o p o x y t r i m e t h y 1 g e r m a n e - h e x a f l u o r o a c e t o n e s o l u t i o n ( F i g -u r e 1) s h o w s d i s t i n c t s e p t e t s a t -3-98 a n d -4.74 p.p.m. a n d m e t h y l a b s o r p t i o n s a t -0.25 a r i d - 0 . 4 3 p.p.m. T h e s e p e a k s a r e a s s i g n e d t o t h e p r o p o x y g e r m a n e a n d i t s 1:1 h e x a f l u o r o a c e t o n e c o m p l e x . I n e x c e s s h e x a f l u o r o a c e t o n e t h e e q u i l i b r i u m s h i f t s i n f a v o u r o f t h e 1:1 c o m p l e x o n l y o n e s e p t e t a t -4-56 p.p.m. ( J = 6 . 1 c p s ) a n d o n e m e t h y l a b s o r p t i o n a t -0.27 p.p.m. a r e p r e s e n t . H e x a f l u o r o p r o p -1 o x y t r i m e t h y l s i l a n e s h o w s s i m i l a r H n . m . r . s p e c t r a t o t h e g e r m a n e 30 i n h e x a f l u o r o a c e t o n e s o l u t i o n ( T a b l e I I ) . 19 T h e ' F n . m . r . s p e c t r a o f h e x a f l u o r o p r o p o x y s i l a n e a n d - g e r m a n e i n e x c e s s h e x a f l u o r o a c e t o n e i s s i m i l a r t o t h a t o f t h e 1:1 h e x a -f l u o r o p r o p o x y t r i m e t h y l t i n - h e x a f l u o r o a c e t o n e c o m p l e x i n h e x a f l u o r o -a c e t o n e , e a c h s p e c t r u m s h o w i n g t w o b r o a d p r o d u c t p e a k s , o n e t o t h e l o w f i e l d s i d e o f h e x a f l u o r o a c e t o n e a n d t h e o t h e r t o t h e h i g h 19 f i e l d s i d e ( s e e T a b l e I I ) . T h e F n . m . r . l o w f i e l d p e a k o f t h e g e r m a n e - h e x a f l u o r o a c e t o n e w a s r e s o l v e d i n t o t w o s e t s o f s e p t e t s w i t h J = 6 c p s a n d J = 2.5 c p s . H - C F ^ CFyCF^ B i s ( h e x a f l u o r o p r o p o x y ) d i m e t h y l t i n f o r m s a s t a b l e 1 : 2 c o m p l e x o w i t h h e x a f l u o r o a c e t o n e a t 20 . ( C H 3 ) 2 S n j 0 C H ( C F 3 ) 2 ~ j 2 + 2 ( G F 3 ) 2 C O > ( C H 3 ) 2 S n | 0 C H ( C F 3 ) ^ 2 - 2 ( C F 3 ) 2 C 0 1 1Q T h i s 1:2 c o m p l e x w a s i d e n t i f i e d f r o m H n . m . r . a n d 7 F n . m . r . s p e c t r a ; I t s *H n.m. r . s p e c t r u m s h o w s a s e p t e t a t -I4..88 p.p.m. ( J = 6 . 0 c p s ) a n d a s i n g l e t a t - 1 . 0 3 p.p.m. ( r e l a t i v e i n t e n s i t y 1 : 2 . 9 ) . I t s ^ F n . m . r . s p e c t r u m s h o w s b r o a d p e a k s a t -2»9br a n d LL .36 p.p.m. f r o m i n t e r n a l h e x a f l u o r o a c e t o n e ( r e l a t i v e i n t e n s i t y 1 : 1 ) . I t w a s a l s o f o u n d t h a t m i x i n g b i s ( h e x a f l u o r o p r o p o x y ) d i -m e t h y l t i n w i t h i t s 1:2 c o m p l e x , ( C H ^ ) 2 S r i | ~ 0 C H ( C F ^ ) J | 2 * 2 ( C F ^ ) ^CO, y i e l d s a new c o m p o u n d w h i c h : . i s a p p a r e n t l y i n e q u i l i ' b r i u r n w i t h t h e r e a c t a n t s . T h i s new c o m p o u n d i s b e l i e v e d t o b e t h e 1:1 c o m p l e x , ( C H 3 ) 2 S n j ^ O C H ( C F 3 ) 2 | 2 ' ( C F 3 ) 2 C O , f o r m e d b y t h e r f e a c t i b h ( C H 3 ) 2 S h p H ( C F 3 ) J j 2 + ( C H 3 ) 2 S n . [ T X H ( C F ^ ) 2 ] 2 * 2 ( G F 3 ) 2 G O ^ 2 , ( C H 3) 2 S n J Q C H (GF 3) J j ? • ( G F ^ ) 2 Q O E v i d e n c e f o r t h i s c o m e s f r o m t h e H i n . m . r . s p e c t r a o f m i x t u r e s o f t h e u n c o m p l e x e d a n d d l c o m p l e x e d b i s p r o p o x y t i n c o m p o u n d w h i c h s h ow t h e a p p e a r a n c e o f a t h i r d m e t h y l p e a k a n d a l s o t h e a p p e a r -a n c e o f a n o t h e r m u l t i p l e t a r o u n d -5 p.p.m-.' T a b l e I I I s h o w s t h a t ( C H 3 ) 3 G e O C H ( C F 3 ) 2 + ( C H ^ G e O C H t C F ^ o ( C F ^ C O r Y w w 7 _L_ 3 1/ e x t T M S p p m o 8 F i g u r e - 1 : H n . m . r . S p e c t r u m o f 2:1 H e x a f l u o r o a c e t o n e - 1,1,1,3,3,3-H e x a f l u o r o p r o p o x y t r i m e t h y l g e r m a n e M o l a r . M i x t u r e . C u r v e 2 i s a n E x p a n s i o n o f t h e D o w n f i e l d M u l t i p l e t s ' • 32 t h e r e l a t i v e i n t e n s i t y o f t h i s new m e t h y l p e a k v a r i e s a s m o r e o f o n e r e a c t a n t i s a d d e d i n d i c a t i n g t h e e s t a b l i s h m e n t o f a n e q u i l i b -r i u m m i x t u r e 3 . T A B L E : I I I lH C H E M I C A L S H I F T S OF ( C H 3 ) 2 S n J l x H l C F ^ J j 2 AND ( C H 3 ) 2 S n J O C H ( C F 3 ) 2 • 2 ( C F 3 ) 2 C O S O L U T I O N S a M o l e r a t i o o f & C H ^ ( p . p . m . ) M e 2 S n X 2 : M e 2 S n X 2 - 2 ( C F 3 ) 2 C O b M e 2 S n X 2 . M e 2 S n X 2 ' ( C F ^ C O M e 2 S n X 2 • 2 ( C F 3 ) 2 C O 0 1 1 2 1 1 - - - 1 . 0 3 2 - 0 . 7 8 ( l ) d - 0 . 9 0 ( b , ) d - 1 . 0 3 ( U ) d 1 . - 0 . 8 0 ( 2 ) d - 0 . 9 K 5 ) d - 1.0LL ( 2 ) d 1 - 0 . 8 3 ( 7 ) d - 0 . 9 2 ( 7 ) d - 1 . 0 5 ( 2 ) d 0 - 0 . 8 L L -3 S p e c t r a r u n o n n e a t l i q u i d s . N e g a t i v e v a l u e s o f £ a r e d o w n f i e l d . 1 3 X = - O C H ( C F 3 ) 2 . ' ^ W i t h r e s p e c t t o e x t e r n a l t e t r a m e t h y l s i l a n e . • T h e a p p r o x i m a t e r e l a t i v e i n t e n s i t y o f t h e m e t h y l a b s o r p t i o n f o r ' a g i v e n s o l u t i o n i s i n p a r e n t h e s i s a f t e r t h e c h e m i c a l s h i f t v a l u e . T h e r e a c t i o n o f d i - n - b u t y l t i n d i h y d r i d e w i t h e x c e s s h e x a -f l u o r o a c e t o n e a l s o g a v e a c o m p l e x w h i c h d e c o m p o s e s a t a p p r o x i m a t e l y _3 . 5 0 ° (10 mm) t o g i v e h e x a f l u o r o a c e t o n e a n d - b i s ( h e x a f l u o r o p r o p o x y ) -d i - n - b u t y l t i n . T h e c o m p l e x c a n be i d e n t i f i e d b y i t s i n f r a r e d s p e c -t r u m w h i c h g i v e s a s t r o n g a b s o r p t i o n a t 970 cm 1 c h a r a c t e r i s t i c o f t h e c o m p l e x e d h e x a f l u o r o a c e t o n e . I t w a s f o u n d ' t h a t t r i f l u o r o a c e t o n e w o u l d n o t c o m p l e x w i t h 1 , 1 , 1 , 3 , 3 , 3 - h e x a f l u o r o p r o p o x y t r i m e t h y l t i n a t 20° a n d t h a t h e x a -f l u o r o a c e t o n e w a s i n e r t \to t r i m e t h y l t i n c h l o r i d e a t 1 2 0 ° . a A n a p p r o x i m a t e e q u i l i b r i u m c o n s t a n t o f \\.% - 2 c a n b e c a l c u l a t e d f o r t h i s r e a c t i o n i f t h e r e l a t i v e i n t e n s i t i e s o f t h e m e t h y l a b -s o r p t i o n i n t h e ^H n . m . r . s p e c t r a a r e u s e d a s a m e a s u r e o f t h e c o n c e n t r a t i o n o f t h e t h r e e s p e c i e s ( T a b l e I I I ) . 33 T o t e s t t h e r e a c t i v i t y o f t h e 1:1 c o m p l e x o f h e x a f l u o r o a c e -t o n e a n d p r o p o x y t r i m e t h y l t i n t h e r e a c t i o n b e t w e e n t r i m e t h y l t i n 1 h y d r i d e a n d t h e 1:1 c o m p l e x w a s f o l l o w e d b y H n . m . r . T h e r e s -u l t ' s s h o w t h a t t h e t i n h y d r i d e v i r t u a l l y d i s a p p e a r s w i t h i n t w o m i n u t e s w i t h t h e a p p e a r a n c e o f t h e m e t h i n e s e p t e t d u e t o h e x a -f l u o r © p r o p o x y t r i m e t h y l t i n . (CH ) S n H + ( C H ) S n O C H ( C F ) • ( C F ) CO — > 2 ( C H ) S n O C H ( C F ) 3 3 3 3 3 2 3 2 3 3 3 2 (2) P r o p o s e d M e c h a n i s m s a n d S t r u c t u r e s A s d e s c r i b e d a b o v e i n t h e r e a c t i o n o f h e x a f l u o r o a c e t o n e w i t h p r i m a r y a n d s e c o n d a r y a r s i n e s , a m i n e s ^ ' a n d u r e a s ^ , t h e p r o d -u c t s c a n be a c c o u n t e d f o r b y p o s t u l a t i n g n u c l e o p h i l i c a t t a c k b y t h e l o n e p a i r o n t h e c a r b o n y l c a r b o n o f t h e k e t o n e . T o a c c o u n t f o r t h e d i r e c t i o n o f a d d i t i o n o f h e x a f l u o r o a c e t o n e t o G r o u p I V h y d r i d e s a r e a c t i o n m e c h a n i s m i n v o l v i n g n u c l e o p h i l i c a t t a c k b y t h e c a r b o n y l o x y g e n o n t h e c e n t r a l m e t a l o r m e t a l l o i d a t o m i s p o s -t u l a t e d . T h u s a f i v e - c o o r d i n a t e d i n t e r m e d i a t e o f t h e t y p e ( C H ^ ) ^ H M O C ( C F ^ ) 2 w o u l d , . b e f i r s t f o r m e d f o l l o w e d b y M-H c l e a v a g e i n d u c e d b y t h e c a r b o n y l c a r b o n f r o m t h e same i n t e r m e d i a t e ( m o s t l i k e l y ) o r f r o m a s e c o n d i n t e r m e d i a t e . N u c l e o p h i l i c a t t a c k h a s o f t e n b e e n s u g g e s t e d a s t h e r e a c t i o n 55 56 57 <?8 57 58 59 r o u t e f o r c o m p o u n d s o f s i l i c o n ^ ^ ' ^ ^ ' ^ '-"'^ f g e r m a n i u n r *^ 58,60 a n d t i n ; i t i s a l s o f o u n d t h a t t i n c o m p o u n d s a r e m u c h m o r e r e a c t i v e t o n u c l e o p h i l e s t h a n s i l a n e s o r g e r m a n e s w h i c h i s c o n -s i s t e n t w i t h t h e p r e s e n t r e s u l t s . I n t h e p r e s e n t i n v e s t i g a t i o n some e v i d e n c e t h a t a f i v e - c o o r d i n a t e d i n t e r m e d i a t e d o e s o c c u r i n t h e h e x a f l u o r o a c e t o n e - h y d r i d e r e a c t i o n s c o m e s f r o m t h e r e s u l t t h a t t h e k e t o n e f o r m s c o m p l e x e s w i t h t h e p r o p o x y d e r i v a t i v e s . T h e c o m p l e x e d h e x a f l u o r o a c e t o n e i s a l m o s t c e r t a i n l y b o u n d t o t h e c e n t r a l m e t a l o r m e t a l l o i d v i a t h e c a r b o n y l o x y g e n . 3U C o m p o u n d s w i t h c a r b o n y l g r o u p s r e a d i l y f o r m c o m p l e x e s w i t h L e w i s a c i d s s u c h a s S n B r , , B F , / 1 ' ^ 2 ' ^ a n d (C, r L ) S n C l a n d i t k 3 k 9 2 2 i s e s t a b l i s h e d t h a t b o n d i n g o c c u r s t h r o u g h t h e o x y g e n a t o m o f t h e c a r b o n y l g r o u p . T h e i n f r a r e d s p e c t r a o f t h e t i n c o m p l e x e s i s o l a t e d i n t h e p r e s e n t i n v e s t i g a t i o n s h o w n o c a r b o n y l a b s o r p t i o n , t h e s p e c -t r a b e i n g c l e a r a b o v e 1375 cm~* e x c e p t f o r C-H s t r e t c h i n g b a n d s . T h u s t h e 1:1 p r o p o x y - h e x a f l u o r o a c e t o n e c o m p l e x e s a r e c o n c l u d e d t o be f i v e - c o o r d i n a t e d . I n t h e o r g a n o m e t a 1 1 i c f i e l d s u c h c o o r d i n a t i o n i s w e l l e s t a b -l i s h e d f o r t i n , t h e n u m b e r o f s t a b l e R ^ S n X ' Y (Y = n u c l e o p h i l e ) K • 1 65 ,66. , .67 ,68 _ . 69 . -c o m p l e x e s b e i n g l a r g e ' ' ' . P u d o v i k a n d c o w o r k e r s f o u n d t h a t t r i e t h y l p h o s p h i n e o x i d e a d d s t o t r i e t h y l t i n i o d i d e t o g i v e a 1:1 a d d u c t w h i c h c a n be d i s t i l l e d i n v a c u u m w i t h o u t d e c o m p o s i t i o n a n d w h i c h i s p r e s u m a b l y s i m i l a r t o t h e 1:1 p r o p o x y - h e x a f l u o r o -a c e t o n e c o m p l e x e s . ( C 2 H ^ ) 3 P O + ( C 2 H ^ ) 3 S n I > ( C 2 H ^ ) 3 P O - S n ( C 2 H ^ ) 3 l R e c e n t l y f i v e - c o o r d i n a t e d s i l i c o n c o m p o u n d s h a v e a l s o b e e n 7 0 i s o l a t e d a l t h o u g h m o s t o f t h e m i n v o l v e t h r e e t o f o u r S i - 0 b o n d s . T h e o n l y p e n t a - c o o r d i n a t e d s i l i c o n s p e c i e s i s o l a t e d c o n -t a i n i n g t w o o r more S i - C b o n d s , . - i s a t r i p h e n y 1 ( b i p y r i d y 1) a i 1 i c o n i u m 7 1 i o n , f o r w h i c h t h e f o l l o w i n g s t r u c t u r e i s p r o p o s e d : C.H r . , 72\73»7i+ T h e r e a r e n u m e r o u s e x a m p l e s o f c o m p l e x e d g e r m a n a t e s , b u t a l m o s t a l l a r e s i x - c o o r d i n a t e d " ' a n d a l l t h e s e c o m p l e x e s h a v e e i t h e r G e - X ( X = h a l o g e n ) , G e - 0 o r - G e - N b o n d s b u t neAe h a v e Ge-C b o n d s . 35 T h e f o r m a t i o n o f a s i x - c o o r d i n a t e d c o m p l e x ( C H ^ ) ^ S n JTJCrUCF^) ^ 2 ( C F 3 ) 2 C O i s e x p e c t e d i n v i e w o f t h e many r e p o r t e d s i x - c o o r d i n -a t e d c o m p l e x e s o f d i a l k y l t i n d i c h l o r i d e s ^ ^ ' ' ' ' ' ^ . I n d i s c u s s i n g t h e s t r u c t u r e o f t h e 1:1 c o m p l e x e s i t s e e m s t h a t t h r e e a l t e r n a t i v e s , I - I T I , s h o u l d b e c o n s i d e r e d . ? 0-C(CF3\ I I +LF\ ( c H ^ M - 0 - C - O - M + O - f - O - f l — 1 3 « + ( C F 3 ) , ( c n i + ( C ^ (^3)3/ I I I S t r u c t u r e I a s s u m e s a l m o s t c o m p l e t e l o c a l i z a t i o n o f t h e p o s i t i v e c h a r g e s i n c e a n y e x t e n s i v e d e 1 o c a 1 i z a t i o n o f c h a r g e t h r o u g h t h e o x y g e n o f t h e c o m p l e x e d k e t o n e w o u l d l e a d t o d i s s o c i a t i o n . T h e c a r b o n i u m i o n w o u l d . b e u n s t a b l e d u e t o t h e a d j a c e n t , h i g h l y e l -e c t r o n e g a t i v e t r i f l u o r o m e t h y 1 g r o u p s , a n d f o r t h i s r e a s o n I i s n o t f a v o u r e d . T h e r e i s some e v i d e n c e f a v o u r i n g s t r u c t u r e I I a n d I I I s i n c e t h e p r o p o x y o x y g e n a p p e a r s t o be a r e l a t i v e l y g o o d e l -e c t r o n d o n o r . T h e m o l e c u l a r w e i g h t o f h e x a f l u o r o p r o p o x y t r i m e t h y 1 -t i n i n b e n z e n e i n d i c a t e s d i m e r f o r m a t i o n . S i m i l a r r e s u l t s h a v e b e e n o b t a i n e d f o r t r i m e t h y l t i n h y d r o x i d e i n c a r b o n t e t r a c h l o r i d e , 77 c h l o r o f o r m o r b e n z e n e . B y a n a l o g y w i t h t h e p r o p o s e d s t r u c t u r e f o r t h e t i n h y d r o x i d e d i m e r t h e p r o p o x y t i n d i m e r c o u l d h a v e t h e f o 1 1 o w i n g s t r u c t u r e ( C U 3 ) 3 S n - - - - 0 CH(CF3\ (CF3\HCO -Sn(cH 3 ^ S t r u c t u r e s I a n d I I I a r e s u p p o r t e d b y t h e *H n. m . r . s p e c t r a o f t h e c o m p l e x e s w h i c h s h o w t h a t t h e t h r e e m e t h y l g r o u p s i n a 36 g i v e n c o m p o u n d h a v e t h e same c h e m i c a l s h i f t . H o w e v e r , t h i s d o e s n o t e x c l u d e I I s i n c e t h e d i f f e r e n c e i n c h e m i c a l s h i f t s e x p e c t e d f o r t h e t h r e e m e t h y l g r o u p s c o u l d b e t o o s m a l l t o be d e t e c t e d . I t i s a l s o p o s s i b l e t h a t r a p i d e x c h a n g e o f t h e m e t h y l g r o u p s f r o m a p i c a l t o t h e e q u a t o r i a l p o s i t i o n ( a s s u m i n g a t r i g o n a l b i p y r a m i d a s t h e s t r u c t u r e ) o c c u r s . T h e b u l k o f t h e n . m . r . e v i d e n c e s u g g e s t s t h a t I i s n o t t h e s t r u c -t u r e . F i r s t l y , i n I I a n d , ' I I I t h e r e s o n a n c e d u e t o t h e p r o t o n o f t h e - C H ( C F ) ^ g r o u p w o u l d b e e x p e c t e d t o be d o w n f i e I d f r o m t h a t i n t h e u n c o m p l e x e d p r o p o x y d e r i v a t i v e b e c a u s e o f t h e p o s i t i v e c h a r g e i n I w o u l d b e e x p e c t e d t o be f o u n d u p f i e l d f r o m t h e ' u n c o m p l e x e d w o u I d . . p r o b a b l y b e d e l o c a l i z e d t o some e x t e n t b y t h e p r o p o x y o x y g e n . T h i s i s n o t f o u n d . T h i r d l y , t h e f l u o r i n e r e s o n a n c e d u e t o t h e c o m p l e x e d k e t o n e i n I I w o u l d be e x p e c t e d t o b e d o w n f i e l d f r o m t h a t o f h e x a f l u o r o a c e t o n e b e c a u s e o f t h e g r e a t e r p o s i t i v e c h a r g e o n t h e c a r b o n a t o m r e s u l t i n g i n a n i n c r e a s e d p a r a m a g n e t i c c o n t r i b u -t i o n . H o w e v e r , t h e r e s o n a n c e i s i n f a c t u p f i e l d f r o m h e x a f l u o r o -19 a c e t o n e . F o u r t h l y , t h e p e a k s i n t h e 7 F n . m . r . s p e c t r u m o f t h e g e r m a n i u m c o m p l e x a r e s p l i t i n t o s e p t e t s ( J j y 2 . 5 c p s ) w h i c h s t r o n g -l y s u g g e s t s f l u o r i n e - f l u o r i n e c o u p l i n g i s p r e s e n t . T h i s c o u l d o c c u r " t h r o u g h s p a c e " , t h r o u g h s i x b o n d s ( a s i n I I a n d I I I ) , o r t h r o u g h e i g h t b o n d s ( a s i n I ) . H o w e v e r , i f t h e g r o u p s i n I a r e c l o s e e n o u g h t o g e t h e r t o c o u p l e " t h r o u g h s p a c e " i t s e e m s l i k e l y o n t h e a d j a c e n t o x y g e n . T h i s i s f o u n d . S e c o n d l y , t h e same p r o t o n c o m p o u n d b e c a u s e o f t h e n e g a t i v e c h a r g e o n t h e c e n t r a l a t o m w h i c h 37 t h a t t h e y w o u l d b e c l o s e e n o u g h t o g e t h e r f o r c y c l i z a t i o n t o t a k e p l a c e t o g i v e I I . T h e m a g n i t u d e o f t h e c o u p l i n g c o n s t a n t a p p e a r s t o f a v o u r c o u p l i n g " t h r o u g h s p a c e " o r t h r o u g h s i x b o n d s 5 . T h e n . m . r . e v i d e n c e f a v o u r s I I o r I I I a n d o f t h e s e t w o s t r u c t u r e I I i s f a v o u r e d o v e r I I I s i n c e i t i s t h o u g h t t h a t I I I w o u l d h a v e a r e l -a t i v e l y h i g h m e l t i n g p o i n t d u e t o i t s p o l y m e r i c s t r u c t u r e . On t h e b a s i s o f I I I ( C H j ) 2 S n |oCH( C F ^ ) £ j 2 * 2 ( C F 3 ) 2 G O w o u I d h a v e f o i i r p o l y m e r i c c h a i n s e x t e n d i n g f r o m t h e t i n a t o m , one f o r e a c h S n - 0 b o n d ( i . e . a t h r e e d i m e n s i o n a l r a t h e r t h a n a l i n e a r p o l y m e r ) , a n d i t i s t h e n e x p e c t e d t h a t t h e 1:2 § i s p r o p o x y t i n - h e x a f l u o r o -a c e t o n e c o m p l e x w o u l d h a v e a h i g h e r m e l t i n g p o i n t t h a n t h e 1:1 p r o p o x y t r i m e t h y l t i n - h e x a f l u o r o a c e t o n e c o m p l e x . H o w e v e r , t h e 1:2 o b i s p r o p o x y t i n - h e x a f l u o r o a c e t o n e c o m p l e x m e l t s a t a p p r o x i m a t e l y 2 0 , T h u s t h e m e l t i n g p o i n t s o f t h e 1:1 a n d 1:2 t i n - h e x a f l u o r o a c e t o n e c o m p l e x e s a p p e a r t o i n d i c a t e a p r e f e r e n c e f o r I I r a t h e r t h a n I I I . I t h a s r e c e n t l y b e e n f o u n d t h a t c h l o r a l a n d o t h e r a l d e h y d e s r e a c t e x o t h e r m i c a 1 l y a n d r e v e r s i b l y w i t h m e t h o x y t r i - n - b u t y l t i n 7 Pi t o g i v e 1:1 a d d i t i o n p r o d u c t s s u c h a s t h e f o l l o w i n g : ( n - C ^ H ^ S n O C H ^ + C C l ^ C H O ^ = = * ( n r C ^ H g J ^ S n C C H t C C l ) 0 C H T h i s 1:1 a d d u c t w i l l t a k e u p a n o t h e r m o l e o f c h l o r a l t o g i v e a p r o d u c t f o r w h i c h t h e f o l l o w i n g s t r u c t u r e i s p r o p o s e d : ( n - C i + H 9 ) 3 S n O C H ( C C l 3 ) O C H ( C C l 3 ) O C H 3 T h i s t y p e o f s t r u c t u r e i s d i s r e g a r d e d f o r t h e h e x a f l u o r o a c e t o n e -p r o p o x y t i n c o m p l e x e s s i n c e t h e e x p e c t e d r e a c t i o n o f t i n h y d r i d e s w i t h t h e l i n e a r c h a i n s t r u c t u r e t o g i v e t h e r e d u c e d a l c o h o l a n d t h e r e d u c e d d i t i n d o e s n o t o c c u r . ( C H 3 ) 3 S n O C ( C F 3 ) 2 O C H ( C F 3 ) 2 + ( C H ^ S n H * ( C H 3 ) 3 S n S n ( C H 3 ) 3 + H O C ( C F 3 ) 2 O C H ( C F 3 ) 2 C o u p l i n g t h r o u g h e i g h t b o n d s w o u l d a l s o i n v o l v e c o u p l i n g t h r o u g h o n e g e r m a n i u m a n d t w o o x y g e n a t o m s a n d t h u s w o u l d be e x p e c t e d t o be n e g l i g i b l e . 38 A s p r e v i o u s l y s t a t e d t h e o n l y r e a c t i o n p r o d u c t f r o m t r i m e t h y l t i n h y d r i d e a n d 1:1 p r o p o x y t i n - h e x a f l u o r o a c e t o n e i s t h e p r o p o x y t i n d e r i v a t i v e . T h e s e r e s u l t s c o u p l e d w i t h t h e m o d e r a t e s t a b i l i t y o f t h e t r i -m e t h y l a r s i n e - h e x a f l u o r o a c e t o n e a n d t h e d i a r s i n e - h e x a f l u o r o a c e t o n e c o m p l e x e s s e e m t o i n d i c a t e t h a t t w o c r i t e r i a a r e n e c e s s a r y f o r s t a b l e c o m p l e x f o r m a t i o n w i t h h e x a f l u o r o a c e t o n e . F i r s t l y , t h e m o l e c u l e m u s t be a b l e t o a c t a s a L e w i s a c i d o r b a s e w i t h r e s p e c t t o t h e o x y g e n o r c a r b o n a t o m o f t h e c a r b o n y l g r o u p a n d s e c o n d l y , i t m u s t b e a b l e t o s t a b i l i z e t h e c o m p l e x f u r t h e r b y d e l o c a l i z i n g t h e c h a r g e p r o d u c e d o n t h e c a r b o n y l g r o u p ( e i t h e r a t t h e o x y g e n o r c a r b o n a t o m s ) o v e r t h e c o m p l e x e d m o l e c u l e . S i n c e t r i f l u o r o a c e t o n e d o e s n o t c o m p l e x w i t h h e x a f l u o r o p r o p -o x y t r i m e t h y l t i n a t 20° i t a p p e a r s t h a t i t m u s t b e a c o n s i d e r a b l y w e a k e r n u c l e o p h i l e t h a n h e x a f l u o r o a c e t o n e . T h i s c a n b e e x p l a i n e d b y a p o s s i b l e s i g n i f i c a n t c o n t r i b u t i o n o f t h e t a u t o m e r i c e n o l f o r m , C F 3 C ( O H ) = C H 2 . I t i s , h o w e v e r , s u r p r i s i n g t o f i n d t h a t t r i m e t h y l t i n c h l o r i d e i s s o i n e r t t o w a r d h e x a f l u o r o a c e t o n e . T r i m e t h y l t i n c h l o r -i d e i s a c o m p o u n d w h i c h f o r m s n u m e r o u s c o m p l e x e s w i t h L e w i s b a s e s a n d i t i s d i f f i c u l t t o s e e w h y t h e f o l l o w i n g s t r u c t u r e w o u l d One p l a u s i b l e a r g u m e n t i s t h a t i n t h e a n a l o g o u s p r o p o x y t i n - h e x a -f l u o r o a c e t o n e c o m p l e x I I t h e e m p t y 2 s p ^ o r b i t a l o n t h e c a r b o n y l -c a r b o n c o u l d b e e x p e c t e d t o o v e r l a p m o r e e f f i c i e n t l y w i t h a f i l -l e d 2 s p 3 o r b i t a l o n o x y g e n t h a n w i t h a f i l l e d 3 s p ^ o r b i t a l o n c h l o r i n e i n t h e a b o v e s t r u c t u r e I V . ( C H ) S n C C H ( C F ) 2 - ( C F ) 2 C O + ( C H J . S n H > 2 ( C H ) S n O C H ( C F j 3 3 3 2 n o t b e s t a b l e . I V 3 9 CHAPTER I I PERFLUOROCYCLOBUTENE AND i,2-DICHLOROTETRAFLUOROCYCLOBUTENE INTRODUCTION The r e a c t i o n of n u e l e o p h i l e s w i t h f l u o r i n a t e d c y c l o a l k e n e s has been the s u b j e c t of a number of i n v e s t i g a t i o n s . In some of th e s e r e a c t i o n i n v o l v e s a t t a c k a t an a l l y l i . c h a l o g e n u»° i> c" s to g i v e s u b s t i t u t i o n a t the a l l y l i c p o s i t i o n . c ^ T * c 2H 5o£?5i-5SH ^  (c2„5o, 2 E F ^ H However, i f a p e r h a l o c y c l o a l k e n e ( f l u o r o and c h l o r o ) i s used nu-o l e o p h i l i c a t t a c k t a k e s p l a c e at' the v i n y l i c h a l o g e n . D i x o n ^ s t u d i e d the a d d i t i o n of l i t h i u m a l k y l and l i t h i u m a r y l r e a g e n t s to p e r f l u o r o c y c l o b u t e n e . L i t h i u m a l k y l s a f f o r d e d both morib-and d i s u b s t i t u t e d p r o d u c t s but o n l y the d i s u b s t i t u t e d d e r i v a t i v e was o b t a i n e d from the a r y l - l i t h i u m r e a c t i o n . R = a l k y l CF=CF0F,CF o + C,H .Li - — > C H C*C(C H )CF_CF_ 2 2 6 5 6 5 6 5 2 2 The a d d i t i o n o f G r i g n a r d r e a g e n t s t o f l u o r i n a t e d c y c l o b u t e n e s has 8 k , 8 5 8 k a l s o been s t u d i e d . Par k and F o n t a n e l l i r e a c t e d b o t h a l k y l and a r y l G r i g n a r d r e a g e n t s w i t h p e r f l u o r o c y c l o b u t e n e and 1 ,2-d i e h l o r o t e t r a f l u o r o c y c l o b u t e n e . A l k y l G r i g n a r d r e a g e n t s and p e r -f l u o r o c y c l o b u t e n e gave m o n o s u b s t i t u t e d d e r i v a t i v e s i n good y i e l d under w i l d c o n d i t i o n s . J ^ C F C F ^ • RMgX — > R ^ S i ^ F . , R - a l k y l U s i n g s t r o n g e r r e a c t i o n c o n d i t i o n s d l a l k y l d e r i v a t i v e s were a l s o formed i n comparable y i e l d s . C 2 H ^ = C F C F 2 C F 2 + CgH^MgBr;. > C 2H^d=C(C 2H^)CF 2CF 2 R e a c t i o n of p e r f l u o r o c y c l o b u t e n e w i t h phenylmagnesium bromide 40 u n d e r m i l d c o n d i t i o n s g a v e b o t h t h e mono- a n d d i p h e n y l d e r i v a t i v e s . On r e a c t i n g 1 , 2 - d i c h l o r o t e t r a f l u o r o c y c l o b u t e n e w i t h a l k y l G r i g -n a r d s t h e m o n o s u b s t i t u t e d p r o d u c t w a s readily f o r m e d . H o w e v e r , f u r t h e r s u b s t i t u t i o n w a s m o r e d i f f i c u l t i n t h i s c a s e t h a n f o r t h e p e r f l u o r o d e r i v a t i v e . I f b r o m i n e o r i o d i n e r e p l a c e d o n e o f t h e o l e f i n i c f l u o r i n e o r c h l o r i n e a t o m s a c o m p e t i n g r e a c t i o n i n v o l v i n g e x c h a n g e o f t h e M g B r g r o u p o c c u r r e d . C F = C B r C F ~ C F 2 + C ^ M g B r C H = C F C F 2 C F 2 + C 2 H ^ C = C B r C F 2 C F 2 T h e b a s e c a t a l y z e d r e a c t i o n o f a l c o h o l s w i t h f l u o r i n a t e d c y -c l o a l k e n e s t o f o r m mono- a n d d i a l k o x y d e r i v a t i v e s h a s a l s o b e e n 86 s t u d i e d . P a r k a n d c o w o r k e r s f o u n d t h a t o n l y t h e d i a l k o x y d e r -i v a t i v e c o u l d b e o b t a i n e d f r o m p e r f l u o r o c y c l o b u t e n e . C F = C F C F 2 C F 2 .+ 2 ROH R O C = C ( O R ) C F 2 C F 2 On . B a r r a n d c o w o r k e r s f o u n d t h a t b y v a r y i n g t h e r e a c t i o n c o n d i t i o n s b o t h mono- a n d d i a l k o x y d e r i v a t i v e s c o u l d b e o b t a i n e d w i t h t h e m o n o a l k o x y d e r i v a t i v e p r e d o m i n a t i n g . ROH . t C F = C F C F 2 C F 2 C ^ H ^ ^ H ^ ^ ^ R O C = C F C F 2 C F 2 + R O C = C ( O R ) C F ^ P h e n o l w a s f o u n d t o g i v e o n l y t h e i n o n o p h e n o x y c o m p o u n d . £ F = C F C F 2 C F 2 + C 6 H ^ O H C 6 H ^ 0 t = C F C F 2 C F 2 88 ^ S t o c k e l a n d c o w o r k e r s o b t a i n e d b o t h t h e mono- a n d d i m e t h o x y d e r i v a t i v e s a s w e l l a s a m e t h o x y k e t o d e r i v a t i v e f r o m t h e b a s e c a t a l y z e d r e a c t i o n o f m e t h a n o l w i t h p e r f l u o r o c y c l o p e n t e n e . C F = C F C F C F C> + C H OH — ^ — • C F = C ( O C H 0 ) C F 0 C F 0 C F 0 2 2 2 3, — - , ^ + C H 3 O C = C ( O C H 3 ) ( C F 2 ) 3 + CH O C = C F C ( 0 ) C F ~ C F 2 W i t h 1 , 2 - d i c h 1 o r o t e t r a f l u o r o c y c l o b u t e n e o n l y t h e m o n o a l k o x y d e r -89 i v a t i v e w a s o b t a i n e d u n d e r n o r m a l r e a c t i o n c o n d i t i o n s . How-e v e r , i f s t r o n g e r r e a c t i o n c o n d i t i o n s w e r e u s e d i n a n a t t e m p t t o r e p l a c e t h e s e c o n d v i n y l i c c h l o r i n e i t w a s f o u n d t h a t t h e a l l y l i c f l u o r i n e s w e r e a t t a c k e d . i n . C _ H , . 0 C = C C l C F o C F o + 2 C H OH -„ • A<_> C H J 3 C = C C IC ( O C H ) „CF„ d i> 2 2 3 t-n^L) d. 5 3 2 2 T h i s r e a c t i o n i s s i m i l a r t o n u c l e o p h i l i c d i s p l a c e m e n t o n o t h e r r e -l a t e d c y c l o b u t e n e s ^ , ^ 1 , ^ , < ^ ' ^ 1 , e . g . CC 1 = C H C F 2 C C 1 2 + 2 C 2 H ^ O H ^ > CC 1=CHCF~C ( O C ^ ) 2 R a p p a n d c o w o r k e r s ' ^ s t u d i e d t h e b a s e c a t a l y z e d r e a c t i o n o f t h i o l s w i t h p e r f l u o r o c y c l o b u t e n e . T h e mono- a n d b i s m e r c a p t o -i c y c l o b u t e n e d e r i v a t i v e s a n d a . d i a d d u c t ( a e y e l o b ' u t a n e ) w e r e i s o -l a t e d . R S H +' C F = C F C F „ C F „ — : * R S C ^ C F C F ^ C F o ' • 2 2 ( C 2 H 5 ) 3 N . 2 2 + R S C = C ( S R ) C F 2 C F 2 + ' R S C F C H ( S R ) C F 2 C F 2 T h e 1 , 2 - b i s m e r c a p t o c y c l o b u t a n e w a s r a t h e r u n s t a b l e a n d d e c o m p -o s e d d u r i n g d i s t i l l a t i o n t o t h e 1 , 2 - b i s m e r c a p t o t e t r a f l u o r o c y c l o -b u t e n e . M e r c a p t o d e r i v a t i v e s o f f l u o r o c y c 1 o a l k e n e s h a v e a l s o b e e n p r e p a r e d f r o m t h e r e a c t i o n o f 1 , 2 - d i c h l o r o p e r f l u o r o c y c l o a l k e n e s 93 w i t h c u p r o u s m e r c a p t i d e s . C 1 C = C C 1 ( C F 0 ) + C u S R —->> R S C = C ( S R ) (CF-_) d n d n n = 2 , 3 o r 4 R = C ^ o r C ^ C H g T h e r e a c t i o n o f p r i m a r y a n d s e c o n d a r y a m i n e s w i t h p e r f l u o r o -c y c l o b u t e n e w a s s t u d i e d b y P r u e t t a n d c o w o r k e r s ^ . . T h e r e s u l t s c a n be r e p r e s e n t e d b y t h e f o l l o w i n g - e q u a t i o n . 2 R 2 N H + i F = C F C F 2 C F _ 2 > R 2 N H 2 F + R 2 N C = C F C F 2 C F 2 R = a l k y l 95 96 M i l l a n d c o w o r k e r s a n d P a r k e r s t u d i e d t h e a d d i t i o n o f a m i n e s t o 1 , 2 - d i s u b s t i t u t e d h e x a f l u o r o c y c l o p e n t e r i e . M i l l e t . at a l . ^ r e a c t e d o n e s u c h c y c l o p e n t e n e w i t h a m m o n i a a n d a n i l i n e t o g e t mono- a n d d i a m i n e d e r i v a t i v e s . C 1 C = C ( C 0 N H 2 ) ( C F 2 ) 3 + 'NH^ — - > N H 2 C = C (CONH' 2)' ( C F g ) ^ Cl.C=CCCONH 2) ( d F 2 ) + C 6 H ^ N H 2 > C 6H^NHC=C ( C O N H 2 ) ( C F 2 ) + C 6 H ^ N H C = C ( C O N H 2 ) C ( N C ^ ) C F 2 C F 2 42 Th-e r e a c t i o n o f p r i m a r y a m i n e s w i t h 1 , 2 - d i c h l o r o h e x a f l u o r o c y c l o -96 ' p e n t e n e g a v e o n l y t h e d i s u b s t i t u t e d p r o d u c t .• C 1 C = G C 1 ( C F 2 ) 3 + R N H 2 > RNHC=CC IC (NR) C F 2 C F 2 9 7 K n u n y a n t s ' r e a c t e d t r i e t h y l p h o s p h i t e w i t h p e r f l u o r o c y c l o b u t e n e a n d o b t a i n e d a m o n o s u b s t i t u t e d p e n t a f l u o r o c y c 1 o b u t e n e c o n t a i n i n g a f i v e c o o r d i n a t e d p h o s p h o r u s a t o m . ( C 2 H ^ O ) P--+ C F = C F C F 2 C F 2 > ( C ^ O ) P ( F ) C = C F C F ' 2 C F 2 C u l l e n a n d H o t a ^ " 1 r e a c t e d t e t r a m e t h y I d i a r s i n e w i t h p e r f l u o r o -c y c l o b u t e n e a n d o b t a i n e d 1 - d i m e t h y l a r s i n o p e n t a f l u o r o c y c l o b u t e n e . G F = C F G F 2 C F 2 + ( C H ^ 2 A S A S ( C H ^ 2 > ( C H 3 ) 2 A s F + ( C H ) 2 A s C = C F C F 2 C F 2 T h e 1 , 2 - d i c h l o r o t e t r a f l u o r o c y c l o b u t e n e a n d 1 , 2 - d i c h l o r o h e x a f l u o r o -98 c y c l o p e n t e h e r e a c t a n a l o g o u s l y w i t h t h e d i a r s i n e T h e o n l y p u b l i s h e d w o r k r e g a r d i n g t h e r e a c t i o n o f G r o u p I V o r g a n o m e t a 1 1 i c c o m p o u n d s w i t h f l u o r o c y c 1 o a l k e n e s i s d e s c r i b e d i n 8 a U . S . p a t e n t . H a l u s k a r e a c t e d some c h l o r o s i l a n e s w i t h a v a r -i e t y o f 1 , 2 - d i c h i o r o p e r f l u o r o c y c l o a l k e n e s a n d 1 - c h 1 o r o f l u o r o -c y c l o a l k e n e s a n d o b t a i n e d 1 - s i l y l c y c l o a l k e n e d e r i v a t i v e s . C H 3 C l 2 S i H + C l 6 = C C l T c F 2 ) 3 -—-> CH^C 1 g S i t = C C 1 ( G F 2 ) ^ • CH C I S i H + F C = C F C F 0 C F 0 . » CH_ :0 1 p S i C = C F C F p C F p 3 2 2 -2?: 3 d _____ C 6 H - j C l - 2 S i H + C 1 C = C H ( C F 2 ) 3 > C 6 H ^ C s l 2 S i C = C H ( C F 2 ) 3 I n t h e p r e s e n t i n v e s t i g a t i o n a s t u d y o f t h e r e a c t i o n s o f . some a r s i n e s a n d G r o u p I V h y d r i d e s w i t h some f l u o r o c y c l o a l k e n e s w a s u n d e r t a k e n a n d t h e r e s u l t s o f t h e s e r e a c t i o n s a r e p r e s e n t e d a n d d i s c u s s e d i n t h e f o l l o w i n g s e c t i o n . 43 E X P E R I M E N T A L T h e g e n e r a l e x p e r i m e n t a l t e c h n i q u e a n d a p p a r a t u s h a v e b e e n p r e v i o u s l y d e s c r i b e d i n C h a p t e r I , p a g e 6. A. A r s i n e s ( 1) S t a r t i n g M a t e r i a l ' s P e r f l u o r o c y c l o b u t e n e , 1 , 2 - d i c h l o r o t e t r a f l u o r o c y c l o b u t e n e , a n d 1 , 2 - d i c h l o r o h e x a f l u o r o c y c l o p e n t e n e w e r e p u r c h a s e d f r o m P e n i n s u l a r C h e m r e s e a r c h I n c . , P.O. B o x 3597* G a i n e s v i l l e , F l o r i d a . T h e y w e r e u s e d w i t h o u t f u r t h e r p u r i f i c a t i o n . T h e p r e p a r a t i o n o f m e t h -y l a r s i n e a n d d i m e t h y l a r s i n e i s d e s c r i b e d i n C h a p t e r I , p a g e 8 . T h e m e t h y l p h e n y l a r s i n e w a s a g i f t f r o m c o w o r k e r D. S. D a w s o n . (2) R e a c t i o n s w i t h t h e C y c l o b u t e n e s a n d t h e C y c l o p e n t e n e ( a ) R e a c t i o n o f M e t h y l p h e n y l a r s i n e a n d P e r f l u o r o c y c l o b u t e n e - -• M e t h y l p h e n y l a r s i n e (3-7 g) a n d p e r f l u o r o c y c l o b u t e n e ( 5 - 2 . g ) w e r e h e a t e d f o r 17 h o u r s a t 1 0 0 ° . P e r f l u o r o c y c l o b u t e n e ( 3 - 3 §) w a s r e c o v e r e d . T h e i n v o l a t i l e p r o d u c t . 1 - m e t h y l p h e n y l a r s i n o p e n t a f l u o r - ' o c y c l o b u t e n e ( 2 . 0 g, 30%) w a s p u r i f i e d b y d i s t i l l a t i o n , b . p . 104° ( 15. mm) , 58° ( 1 0 ~ 3 mm) ( F o u n d : C* 4 2 . 8 ; H, 2 . 1 ; A s , 2 4 * 4 ; ' F, 3 0 . 8 % . C a l c . f o r C j j H g A s F ^ : C, 4 2 . 6 ; H, 2 . 6 ; A s , - 2 4 . 2 ; F, 3 0 . 6 %) . I n f r a -r e d s p e c t r u m ( 1 i q u i d : f i l m ) : 3090 m, 3055 m, 2940 w, 1659 s , 1584 w, 1488 m, 1441 m, 1420 w, 1389 s , 1373 rn> 1333 w, 1303 w ( s h ) , 1293 w ( s h ) , 1274 v s , 1205 s, 1115 v s , 1079 m, 1069 w ( s h ) , 1024 m, 1001 m, 947 s, 853 m, 810 s , 735 s , 692 s , 646 m c m - 1 . N.m.r. 19 s p e c t r a : t h e F n. m . r . s p e c t r u m s h o w e d m u l t i p l e t s a t 2 7 . 5 » 33-7? a n d 3 9 . 7 p . p v m . o f r e l a t i v e i n t e n s i t i e s 1 : 2 : 2 . ( b ) R e a c t i o n o f D i m e t h y l a r s i n e a n d 1 , 2 - D i c h l o r o t e t r a f l u o r o -c y c l o b u t e n e - - ; D i m e t h y l a r s i n e ( 2 . 4 g) a n d 1 , 2 - d i c h l o r o t e t r a f l u o r o c y c l o b u t e n e ( 6 . 9 g) w e r e h e a t e d a t 100° f o r 5 d a y s . H y d r o g e n c h l o r i d e ( 0 . 8 5 g, 100%) o f m o l e c u l a r w e i g h t 3 6 . 5 ( C a l c : 3 6 . 5 )> w h i c h w e n t t h r o u g h a 44 - 9 6 ° t r a p , w a s i s o l a t e d . U n r e a c t e d b u t e n e ( 2 . 6 g) w a s r e c o v e r e d a n d t h e r e a c t i o n p r o d u c t , l - c h l o r o - 2 - d i m e t h y l a r s i n o t e t r a f l u o r o -98 ' c y . c l o b u t e n e {$.Q c)i 97%), o f k n o w n i n f r a r e d s p e c t r u m c o n d e n s e d i n a - 2 3 ° t r a p . ( c ) R e a c t i o n o f l - C h l o r o - 2 - d i m e t h y l a r s i n o t e t r a f l u o r o c y c l o -b u t e n e a n d D i m e t h y l a r s i n e - - . • D i m e t h y l a r s i n e ( 2 . 1 g) a n d t h e d i m e t h y l a r s i n o c y c l o b u t e n e ( 8 . 0 g) w e r e h e a t e d a t II4.O0 f o r 3 d a y s . A v o l a t i l e f r a c t i o n w a s o b t a i n e d w h i c h c o n t a i n e d n o A s - H a b s o r p t i o n a n d w h i c h w h e n c o n d e n s e d i n t o a n a q u e o u s s i l v e r n i t r a t e s o l u t i o n f o r m e d a p r e c i p i t a t e w h i c h l a t e r t u r n e d t h e c h a r a c t e r i s t i c m a u v e c o l o u r o f s i l v e r c h l o r i d e . U n -r e a c t e d d i m e t h y 1 a r s i n o c y c l o b u t e n e ( 4 - 9 g) w a s r e c o v e r e d i n a - 2 3 ° t r a p . T h e i n v o l a t i l e r e a c t i o n p r o d u c t r e m a i n i n g i n t h e C a r i u s t u b e w a s d i s t i l l e d i n a n i t r o g e n a t m o s p h e r e t o g i v e l r 2 - b i s ( d i -m e t h y l a r s i n o ) t e t r a f i u o r o c y c l o b u t e n e , b . p . 120° (47 mm), ( 3 - 5 g» 52%) ( F o u n d : C, 2 8 . 7 ; H, 3 . J 4 ; A s , I4.I4.. 8;. F, 2 3 . 0 %, m o l . wt, ( c a m -p h o r ) , 3 2 0 . G a l e , f o r C g H ^ A s F ^ : C, 2 8 . 6 ; H, 3 . 6 ; A s , 4 4 - 6 ; F, 2 3 . 2 %', m o l . w t . , 3 3 6 ) . T h i s b i s a r s i n o c y c l o b u t e n e s l o w l y o x i d -i z e d i n a i r . I n f r a r e d - s p e c t r u m ( l i q u i d f i l m ) : 3000 m, 2920 m, 28.10 w, • 2105 w, 1913 w, 1420 s, 1329 m, 1300 v s , 1263 s , 121+6 m, 1225 vs., 1154 v s , 1130 s , 1084 v s , 897 s, 859 s, 845 s, 803 s c m - 1 . ( d ) R e a c t i o n o f D i m e t h y l a r s i n e a n d 1 , 2 - D i c h l o r o h e x a f l u o r o -c y c l o p e n t e n e - - \ . D i m e t h y l a r s i n e ( 2 . 3 g) a n d t h e c y c l o p e n t e n e (7 -9 g) w e r e h e a t e d a t 100° f o r 2 d a y s . A m i x t u r e o f d i m e t h y l a r s i n e a n d h y d r o g e n c h l o r -i d e ( 1 . 3 g) w a s o b t a i n e d w h i c h c o u l d n o t be s e p a r a t e d b y t r a p - t o -t r a p d i s t i l l a t i o n . U n r e a c t e d d i c h l o r o h e x a f l u o r o c y c l o p e n t e n e ( 5 . 0 g) s t o p p e d i n a - 4 6 ° t r a p . T h e r e a c t i o n p r o d u c t w h i c h r e m a i n e d i n t h e C a r i u s t u b e w a s i d e n t i f i e d a s l - c h l o r o - 2 - d i m e t h y l a r s i n o h e x a -98 f l u o r o c y c l o p e n t e n e (3.-9 9, 55%) b y i t s k n o w n i n f r a r e d s p e c t r u m 45 ( e ) R e a c t i o n o f D i m e t h y l a r s i n e a n d P e r f l u o r o p r o p e n e - - D i m e t h -y l a r s i n e (1.8 g) a n d p e r f l u o r o p r o p e n e ( 1 1 . 0 g) w e r e h e a t e d a t 100° f o r 5 d a y s . U n r e a c t e d p e r f l u o r o p r o p e n e ( 9 . 3 g) w h i c h w e n t t h r o u g h a - 6 4 ° t r a p w a s r e c o v e r e d . T h e r e m a i n i n g m a t e r i a l ( 3 . 6 g) w h i c h c o n d e n s e d i n a - 6 4 ° t r a p w a s p u r i f i e d b y v . p . c . ( 5 ' U c o n P o l a r c o l u m n a t 1 1 0 ° ) . T h e r e a c t i o n p r o d u c t , 2 r H - 1 - d i m e t h y l a r s i n o h e x a -f l u o r o p r o p a n e h a d a b o i l i n g p o i n t o f 1 1 0 - 1 1 1 ° (739 mm) ( F o u n d : C, 2 3 - 4 ; H, 2 . 8 ; A s , 2 9 . 4 ; F, 44-3 %• C a l c . f o r O A s F : C, 2 3 . 2 ; b 7 6 H, 2 . 7 ; A s , 2 9 ' . 3 ; F, 4 4 - 5 %).-.' I n f r a r e d s p e c t r u m ( v a p . o u r ) : 3090 w, 3030 w, 1424 w, 1381 s , 1290 s , 1212 v s , 1178 v s , 1105 s , 1077 s, 1005 w, 980 vw, 937 w, 904 w, 878 w, 854 m, 791 w, 717 m, 678 m c m - 1 . T h e r e a c t i o n p r o d u c t , 2 - H - 1 - d i m e t h y l a r s i n o h e x a f l u o r o p r o p a n e , w a s h e a t e d a t l 8 0 ° f o r 21 h o u r s . T h e C a r i u s t u b e s h o w e d n o ' s i g n s o f e t c h i n g a n d t h e r e c o v e r e d a r s e n i c c o m p o u n d w h i c h s t o p p e d i n a - 6 4 ° t r a p s h o w e d n o t r a c e o f d o u b l e 1 b o n d a b s o r p t i o n i n t h e i n f r a -r e d s p e c t r u m . ' ( f ) R e a c t i o n o f t h e D i m e t h y l a r s i n o h e x a f l u o r o p r o p a n e a n d B r o m i n e - - T h e a r s i n o p r o p a n e ( 1.0 g) , b'Tom'ine ( 2 . 3 g) a n d c a r b o n t e t r a c h l o r -i d e ( 1 . 8 g) w e r e l e f t t o r e a c t a t r o o m t e m p e r a t u r e f o r 3 w e e k s . M e t h y l b r o m i d e ( 0 . 7 g) w h i c h w e n t t h r o u g h a -96 t r a p w a s p r o d -u c e d a n d w a s i d e n t i f i e d b y i t s k n o w n i n f r a r e d s p e c t r u m . T h e r e -m a i n i n g v o l a t i l e m a t e r i a l ' ( 3 - 2 g) w a s a d d e d t o m e r c u r y t o r e m o v e t h e e x c e s s b r o m i n e . T h e c a r b o n t e t r a c h l o r i d e w a s r e m o v e d b y a , - 7 8 Q t r a p a n d 2 - H - 1 - b r o m o h e x a f l u o r o p r o p a n e w a s i d e n t i f i e d by i t s 99 k n o w n i n f r a r e d s p e c t r u m a n d i t s m o l e c u l a r w e i g h t of 227 ( C a l c : 231). (3) *H n .m.r. S t u d i e s o f D i m e t h y l a r s i n e a n d t h e F l u o r o c y c 1 o b u t e n e s a t 20° •  ( a ) D i m e t h y l a r s i n e a n d P e r f l u o r o c y c l o b u t e n e - - E x c e s s e y e l o -b u t e n e a n d d i m e t h y l a r s i n e w e r e s e a l e d i n a n n . m . r . ! t u b e . T h e *H n . m . r . s p e c t r u m w i t h i n 30 m i n u t e s a f t e r m i x i n g s h o w e d t h e a p p e a r a n c e 46 o f a s e c o n d m e ' t h y l p e a k a t - 1 . 0 0 p.p.m. ( t h e m e t h y l a b s o r p t i o n o f ( G H ^ ) ^ A s H i s a d o u b l e t a t - 0 . 6 9 p.p.m.) w h i c h w a s a p p r o x i m a t e l y 0.5% t h e i n t e n s i t y o f t h e d i m e t h y l a r s i n e p e a k s . A f t e r 24 h o u r s t h e r e a c t i o n w a s o n e t h i r d c o m p l e t e ; n o d o w n f i e l d p r o t o n w a s p r e s -e n t a n d a t h i r d a b s o r p t i o n i n t h e m e t h y l r e g i o n a t - 0 . 8 4 p-P-m. r e p r e s e n t e d a p p r o x i m a t e l y 1.5% o f t h e t o t a l m e t h y l a b s o r p t i o n i n t -e n s i t y . A f t e r 4 d a y s t h e r e a c t i o n w a s 85% c o m p l e t e w i t h t h e t h i r d m e t h y l a b s o r p t i o n r e p r e s e n t i n g 3% o f t h e p r o d u c t , 1 - d i m e t h y l a r s - ' i n o p e n t a f l u o r o c y c l o b u t e n e , p e a k a r e a . ( b ) D i m e t h y l a r s i n e a n d 1 , 2 - D i c h l o f o t e t r a f l u o r o c y c l o b u t e n e - -T h e *H n.m.r. s t u d y o f t h i s r e a c t i o n s h o w e d t h a t i t w a s s u b s t a n -t i a l l y s l o w e r a t 20° b e i n g o n l y 19% c o m p l e t e a f t e r 6 d a y s a n d 36% c o m p l e t e a f t e r 12 d a y s . T h e m e t h y l a b s o r p t i o n o f t h e p r o d u c t , l - c h l o r o - 2 - d i m e t h y l a r s i n o t e t r a f l u o r o c y c l o b u t e n e , w a s a t - 1 . 11 p.p.m. a n d a f t e r 12 d a y s t h e m e t h y l a b s o r p t i o n o f d i m e t h y l a r s i n e w a s a s i n g l e t a t - 0 . 8 l p.p.m. B. G r o u p I V H y d r i d e s ( 1) S t a r t i n g M a t e r i a l s T h e p r e p a r a t i o n o f t r i m e t h y l g e r m a n e a n d t h e t i n h y d r i d e s i s 1 d e s c r i b e d i n C h a p t e r I , p a g e s 13-14-' ( 2) R e a c t i o n s w i t h t h e C y c l o b u t e n e s a n d C y c l o p e n t e n e ( a ) R e a c t i o n o f T r i m e t h y l s i l a n e a n d 1 , 2 - D i c h l o r o t e t r a f l u o r o -c y c l o b u t e n e -- T r i m e t h y l s i l a n e ( 2 . 4 g) a n d t h e b u t e n e ( 1 1 . 5 g) w e r e h e a t e d a t 190° f o r 12 h o u r s . A n o n - c o n d e h s i b 1 e g a s w a s p r o d u c e d a n d i d e n t -i f i e d a s h y d r o g e n f r o m i t s m o l e c u l a r w e i g h t o f 3 ( C a l c : 2 . 0 ) . T r a p - t o - t r a p d i s t i l l a t i o n g a v e t h e f o l l o w i n g f r a c t i o n s : h y d r o g e n c h l o r i d e ( 0 . 3 4 g) w h i c h w e n t t h r o u g h a - 1 3 6 0 t r a p a n d w h i c h w a s i d e n t i f i e d b y i t s m o l e c u l a r w e i g h t o f 3 6 . 5 ( C a l c : 3 6 . 5 ) ; a m i x -t u r e o f t r i m e t h y l s i l a n e a n d t e t r a m e t h y 1 s i l a n e ( 0 . 3 9> m o l . wt., 82) 1+7 , o w h i c h c o n d e n s e d i n a -136 t r a p a n d w h i c h w a s i d e n t i f i e d b y i t s i n f r a r e d s p e c t r u m . T h i s l a t t e r f r a c t i o n c o u l d n o t be s e p a r a t e d i n t o i t s s e p a r a t e c o m p o n e n t s b y f u r t h e r t r a p - t o - t r a p d i s t i l l a t i o n . A - 7 8 ° f r a c t i o n ( 8 . 5 g) c o n s i s t i n g o f u n r e a c t e d c y c l o b u t e n e a n d c h l o r o t r i m e t h y l s i l a n e c o u l d n o t b e s e p a r a t e d b y d i s t i l l a t i o n ; t h e e n t i r e f r a c t i o n b o i l e d b e t w e e n 6 0 Q a n d 7 0 ° . T h i s f r a c t i o n w a s a d d e d t o a n a q u e o u s s o l u t i o n o f s i l v e r n i t r a t e a n d s i l v e r c h l o r i d e ( 1 . 8 g) w a s p r o d u c e d . P u r e 1 , 2 - d i c h l o r o t e t r a f l u o r o c y -c l o b u t e n e w a s f o u n d t o be u n a f f e c t e d b y a n a q u e o u s s i l v e r n i t r a t e s o l u t i o n . T h e m a i n r e a c t i o n p r o d u c t , 1 - c h l o r o - 3 , 3 > l+» h~ t e t r a f l u o r -o c y c l o b u t e n y l t r i m e t h y l s i l a n e (1+.5 g, 60%) c o n d e n s e d i n a - 2 3 ° t r a p a n d w a s p u r i f i e d b y d i s t i l l a t i o n , b . p . 132° (762 mm) ( F o u n d : C, 3 6 . 1 ; H,' 3 • 9» C I , 1 5 . 5 ; F, 3 2 . 7 %> C a l c . f o r ^ H ^ C l F ^ S i : C, 3 6 . 1.; H, 3 . 9 ; C I , 1 5 . 2 ; F, 3 2 . 7 %). I n f r a r e d s p e c t r u m ( l i q u i d f i l m ) : 2972 m, 2905 w, 1576 s, 11+19 m, 133k v s , - 1256 m ' ( s h ) , 121+2 v s , 1 1 7 l + w ( s h ) , 1151+ w ( s h ) , 1132 m ( s h ) , l l l 6 v s , 1 0 1 3 w , 91+8 w, 81+8 v s , 809 s , 76k m, 715 m, 626 m c m - 1 . ('b) R e a c t i o n o f T r i m e t h y l s i l a n e a n d P e r f l u o r o c y c l o b u t e n e - -T r i - m e t h y l s i l a n e ( 7 - 3 g) a n d p e r f l u o r o c y c l o b u t e n e ( 5 - 5 g) w e r e h e a t e d a t 250° f o r k d a y s . A n o n - c o n d e n s i b l e g a s w a s p r o d u c e d w h i c h w a s i d e n t i f i e d a s h y d r o g e n b y i t s m o l e c u l a r w e i g h t o f 2 .1 ( C a l c : 2 . 0 ) . S l i g h t l y i m p u r e t r i m e t h y l s i l a n e ( 5 - 9 g) Was r e c o v -e r e d . A s e c o n d f r a c t i o n ( 5 - 5 g) w h i c h c o n d e n s e d i n a - 6 k ° t r a p w a s d i s t i l l e d a t 756 mm, t h e m a i n p o r t i o n c o m i n g o f f a t 112 . I n f r a r e d s p e c t r u m o f 1 1 2 ° f r a c t i o n ( 1 i q u i d f i l m ) : 2995 m, 2925 w, 1398 s , 1333 s , 1281 m, 121+0 v s , 1177 v s , I I 6 7 m, 110k m, 1037 s , 1001 s, 956 v s , 858 s, 831 m, 776 m, 766 w ( s h ) , 700 w cm" 1. N.m.r. s p e c t r a : t h e *H n.m.r. s p e c t r u m h a d a s i n g l e t a t 0 . 0 2 p.p.m. (-CH,) a n d a p e a k a t -1+.93 p.p.m. w h i c h w a s a d o u b l e t ( J = 48 . 52 c p s ) s p l i t i n t o f u r t h e r p e a k s . T h i s f r a c t i o n ( b . p . 1 1 2 ° ( 7 5 ° mm)) c o u l d n o t b e p u r i f i e d b y v . p . c . ( 5 ' d i n o n y l p h t h a l a t e a t 70°) b e c a u s e o f r a p i d h y d r o l y s i s o f t h e c o m p o u n d . A l t h o u g h m o l e c u l a r w e i g h t m e a s u r e m e n t s ( F o u n d : 2 3 7 , 2 4 0 ; C a l c . f o r C - H ^ F ^ S i : 236) w e r e s a t i s f a c t o r y f o r 1 , 2 , 3 , 3 , 4 , 4 _ h e x a f l u o r o c y c l o b u t y l t r i m e t h y 1 s i l a n e , t h e e l e m e n t a l m i c r o - , a n a l y s i s w a s n o t s a t i s f a c t o r y . A t h i r d f r a c t i o n ( 1 . 3 g) w h i c h c o n d e n s e d i n a - 2 3 ° t r a p w a s s h o w n t o c o n t a i n a m i n i m u m o f 5 c o m p o n e n t s b y v . p . c . (5* d i n o n y l p h t h a l a t e a t 100°) n o n e o f w h i c h w e r e i d e n t i f i e d . ( c ) R e a c t i o n o f T r i m e t h y l g e r m a n e a n d P e r f l u o r o c y c l o b u t e n e - -T h e g e r m a n e ( 1 . 2 G .3) a n d t h e c y c l o b u t e n e ( 9 - 3 6 g) w e r e h e a t e d a t 2 3 0 O f o r 3 d a y s . U n r e a c t e d p e r f l u o r o c y c l o b u t e n e ( 8 . 0 5 g) > w h i c h w e n t t h r o u g h a - 7 8 ° t r a p , -was r e c o v e r e d . A s e c o n d f r a c t i o n (2.46 g ) w h i c h c o n d e n s e d i n a - 7 8 0 t r a p w a s i d e n t i f i e d a s 1 , 2 , 3 , 3 » 4 » 4 _ h e x a -f l u o r o c y c l o b u t y l t r i m e t h y l g e r m a n e , b . p . 1 1 8 ° (752 mm) ( F o u n d : C, 2 9 - 7 ; H, 3 - 8 %. C a l c . f o r . C 7 H 1 0 F 6 G e : C, 2 9 . 9 ; H, 3-6 %) . I n f r a -r e d s p e c t r u m ( v a p o u r ) :• 3000 w, 2930 w, 1424 w, 1398 s , 1334 s> 1282 m, 1241 v s , 1185 v s , I I 6 3 m, l l O O i m , 1035 s, 1003 s , 959 v s , 829 v s , 771 m, 753 w ( s h ) , 714 w c m " 1 . N.m.r. s p e c t r a : . t h e *H n .m.r. s p e c t r u m s h o w e d a s i n g l e t a t - 0 . 2 5 p.p.m. (-CH^) a n d a p e a k a t - 5 - 0 1 p.p.m. w h i c h w a s a d o u b l e t ( J = 55 c p s ) s p l i t i n t o f u r t h e r p e a k s . T h e r e l a t i v e i n t e n s i t y o f t h e m e t h y l p e a k t o t h e i m u l t i p l e t w a s 1 :9-3 ( C a l c . 1 : 9 . 0 ) . ( d ) R e a c t i o n o f T r i m e t h y l g e r m a n e a n d 1 , 2 - D i c h l o r o t e t r a f l u o r o -c y c 1 o b u t e n e T h e g e r m a n e ( 3 - 4 g) a n e * t h e d i c h l o r o b u t e n e ( 6 . 6 2 g) w e r e h e a t e d a t 190° f o r 36 h o u r s . " T h e m o r e v o l a t i l e f r a c t i o n w h i c h w e n t t h r o u g h a - 4 6 ° t r a p s h o w e d a Ge-H i n f r a r e d a b s o r p t i o n a n d w a s t r a n s f e r r e d t o a C a r i u s t u b e a n d h e a t e d a t 230° f o r 3 d a y s . A 49 f r a c t i o n ( 1 . 3 g) w h i c h c o n d e n s e d i n a -I4.6 0 t r a p c o u l d n o t be f u r -t h e r s e p a r a t e d b y t r a p - t o - t r a p d i s t i l l a t i o n . T h e -14.60 f r a c t i o n a l s o c o u l d n o t be s e p a r a t e d b y a t m o s p h e r i c d i s t i l l a t i o n a n d w a s o s e p a r a t e d b y v . p . c . ( 1 0 ' s i l i c o n e c o l u m n a t 170 ) . T h e v . p . c . s p e c t r u m s h o w e d 6 c o m p o n e n t s . T h e f i r s t c o m p o n e n t (20% b y w e i g h t ) w a s f o u n d t o be c h l o r o -t r i m e t h y l g e r m a n e a s i d e n t i f i e d by i t s i n f r a r e d s p e c t r u m a n d i t s b o i l i n g p o i n t o f 102° ( l i t . v a l u e 102°) ( F o u n d : C, 2 3 . 9 ; H, $.9,%. C a l c . f o r C ^ H g C l G e : C, 2 3 - 5 ; H, 5 -9 % ) . T h e s e c o n d c o m p o n e n t {0.%% b y w e i g h t ) h a d t h e f o l l o w i n g *H n . m.r. a n d / i n f r a r e d s p e c t r a . I n f r a r e d s p e c t r u m ( C C l ^ s o l u t i o n ) : 3015 w, 2930 w, 1865 vw, 1825 vw, 1743 vw, 1420 w, 1333 s, 1261 s , 1168 s, 1130 m, 1117 v s , 1091 m, 903 w, 871 w, 833 s c m " 1 . N.m.r. s p e c t r a : t h e *H n . m . r . s p e c t r u m o f a 20% s o l u t i o n i n c a r b o n t e t r a -c h l o r i d e s h o w e d a s i n g l e t a t - 0 . 3 3 p.p.m. (-CH ) a n d a t r i p l e t a t - 6 . 7 9 p.p.m. ( J = 9 . 5 c p s ) o f r e l a t i v e i n t e n s i t y 1 : 8 . 9 ( C a l c . f o r ( C H ^ ) 3 G e f c = C H C F 2 C F 2 : 1 : 9 . 0 ) . T h e t h i r d c o m p o n e n t (40% b y w e i g h t ) w a s i d e n t i f i e d a s 1-c h l o r o t e t r a f l u o r o c y c l o b u t e n y 1 - 2 - t r i m e t h y l g e r m a n e , b . p . 7 8 ° (50 mm) ( F o u n d : C, 2 9 - 9 , H, 3-7 %. C a l c . f o r C H C l F , G e : C, 3 0 . 3 ; H, 7 9 4 3 . 3 %). I n f r a r e d s p e c t r u m ( l i q u i d f i l m ) : 3005 w, 2925 w, 2825 vw, 1822 vw, 1576 s , 1419 m, 138O w, 1358 w ( s h ) , 1333 v s , 1241 v s , Tl70 w ( s h ) , 1145 w - { s h ) , 1112 v s , 847 s , 834 m ( s h ) , 810 m, 772 m -1 1 cm . N.m.r. s p e c t r a : t h e H n .m.r. s p e c t r u m . s h o w e d a s i n g l e p e a k a t - 0 . 2 1 p.p.m. ( - C H ^ ) . T h e f o u r t h c o m p o n e n t (4% b y w e i g h t ) h a d t h e f o l l o w i n g *H n . m.r. a n d i n f r a r e d s p e c t r a . I n f r a r e d s p e c t r u m ( l i q u i d f i l m ) : 3017 w, 2950 w, 1420 w, 1354 s, 1282 m, 1261 m, 1201 s , 1164 s, 1135 s , 1099 m, 1050 m, 1010 m, 954 ™, 832 s , 771 m c m " 1 . N.m.r. 50 1 s p e c t r a : t h e . H n.m.r. s p e c t r u m o f a 30% s o l u t i o n i n c a r b o n t e t -r a c h l o r i d e s h o w e d a s i n g l e t a t ' -O . '3'l p.p.m. (-CH-J a n d m u l t i p l e t s a t - 2 . 3 a n d -4«05 p.p.m. o f r e l a t i v e i n t e n s i t y 9 : 0 . 9 * I ( C a l c . f o r ( C H ^ y j - C H - C H C l C F - C F - : 9 : 1 : 1 ) . T h e f i f t h c o m p o n e n t (8%: b y w e i g h t ) w a s i d e n t i f i e d a s 1 - c h l o r o -3 , 3 » 4 , k - t e t r a f l u o r o c y c l o b u t y l - 2 - t r i m e t h y l g e r m a n e , b . p . 80-82° (50 mm) ( F o u n d : C, 3 0 . 3 * H, 3 . 8 ; G e , 25 .6 ' ; F, 2 7 . 4 ; C I , 1 2 . k %. C a l c . f o r C - , H 1 1 C l F [ | G e : C, 3 0 . 1 ; H, 4 . 0 ; Ge, 2 6 . 0 ; F, 2 7 - 2 ; C I , 12.7 %) • I n f r a r e d s p e c t r u m ( l i q u i d f i l m ) : 300k w, 2930 w, l k l 6 w, 1351 s, 1279 m, 1244 m, 1213 s , 1163 w, 1134 s, 1082 s , 1059 w, 1025 w, 949 m, 831 s, 817 m, 769 w cm N.m.r. s p e c t r a : i t s *H n.m.r. s p e c t r u m s h o w e d a s i n g l e t a t - 0 . 2 9 p.p.m. (-CH ') a n d m u l t i p l e t s a t - 2 . 5 7 a n d - 4 - 5 6 p.p.m.. o f r e l a t i v e i n t e n s i t y 9 : 1 : 0 . 9 ( C a l c . : 9 : 1 : 1 ) . T h e s i x t h c o m p o n e n t (27% b y w e i g h t ) , b . p . 86° (50 mm), h a d t h e f o l l o w i n g *H n.m . r . a n d i n f r a r e d s p e c t r a . I n f r a r e d s p e c t r u m ( C C l ^ s o l u t i o n ) : 3008 w, 2930 w, 2827 vw, lk . 19 w, 1356 s , 1276 m, 1250 w, 1245 s , 1219 s, 1179 s, 1145 m, 1124 s , 1105 m, 1073 m, 1 0 3 0 m , 959 m, 875 s , 836 s , 690 vw c m - 1 . N.m.r. s p e c t r a : t h e 1 . H n . m . r . s p e c t r u m o f a 20% s o l u t i o n i n c a r b o n t e t r a c h l o r i d e s h o w e d a s i n g l e t a t - 0 . 4 9 p.p.m. (-CH ) a n d a s e p t e t a t - 4 - 5 4 p.p.m. ( J = 4 c p s ) o f r e l a t i v e i n t e n s i t y 1 : 9 . 2 ( C a l c . f o r ( C H ^ ) ^ G e C C I C C l H C F 2 i F 2 : 1 : 9 . 0 ) . T h e m a t e r i a l w h i c h w a s h e a t e d a t 230° f o r 3 d a y s c o u l d n o t be s e p a r a t e d b y v a c u u m o r h i g h p r e s s u r e d i s t i l l a t i o n s . A f r a c -t i o n ( 0 . 2 2 g) w h i c h w e n t t h r o u g h a - 7 8 ° t r a p w a s a d d e d t o a n a q u e o u s s o l u t i o n o f s i l v e r n i t r a t e a n d a c u r d y p r e c i p i t a t e a p -p e a r e d . T h e - 7 8 ° f r a c t i o n ( 3 - 0 2 g) w h i c h w e n t t h r o u g h a - 4 6 ° t r a p w a s s h o w n b y i n f r a r e d a n a l y s i s t o c o n t a i n t w o a b s o r p t i o n s i n 51 , t h e d o u b l e b o n d r e g i o n a t 6 . 1 u (C 1 C = C C l C F ^ F ^ ) a n d 6 . 3 / ( . A o v . p . c . a n a l y s i s o f t h e -1+6 f r a c t i o n (5«5 g) s h o w e d f i v e c o m p -o n e n t s ; t h e s i x t h c o m p o n e n t w h i c h w a s p r e s e n t i n t h e 190° r e a c -t i o n w a s a b s e n t i n t h i s c a s e . C o m p o n e n t s 1 , 2 , 3,4 a n d 5 w e r e i n r a t i o . 5 " 1 ' 1 0 : 1 : 2 r e s p e c t i v e l y b y w e i g h t . ( e ) R e a c t i o n o f T r i m e t h y l t i n H y d r i d e a n d P e r f l u o r o c y c l o b u t e n e - - T r i m e t h y l t i n h y d r i d e (2.4 g) a n d t h e c y c l o b u t e n e ( 3 - 3 g) w e r e l e f t a t r o o m t e m p e r a t u r e f o r 4 d a y s . T h e r e a c t i o n m i x t u r e t u r n e d c l o u d y a l m o s t i m m e d i a t e l y a n d a t t h e e n d o f 4 d a y s a s o l i d ( 0 . 2 g) w a s p r o d u c e d . U n r e a c t e d p e r f l u o r o c y c 1 o b u t e n e ( 1 . 1 g) w i t h a t r a c e o f 1 - H - p e n t a f l u o r o c y c l o b u t e n e , w h i c h w e n t t h r o u g h a - 4 6 ° t r a p , w a s r e c o v e r e d . T h e m a i n r e a c t i o n p r o d u c t , 1 , 2 , 3 , 3 > 4 > 4 ~ n e x a -f l u o r o c y c 1 o b u t y l t r i m e t h y l t i n ( 4 - 4 g)> c o n d e n s e d i n a - 4 6 ° t r a p . I n f r a r e d s p e c t r u m ( - l i q u i d f i l m ) : 2985 vw, 2950 m, 1390 s, 1329 s , 1273 m, 1235 s , 1172 v s , 1150 m, 1091 m, 1056 vw, 1018 s , 999 s , 949 v s , 830 m, 782 s, 769 m, 72*6 w c m " 1 . N.m.r. s p e c t r a : i t s *H n.m.r.. s p e c t r u m s h o w e d a s i n g l e t a t - 0 . 2 8 p.p.m. (-CH-j) a n d a. d o u b -l e t a t -5 -10 p.p.m. ( J = 5 5 c p s ) w h i c h w a s f u r t h e r s p l i t i n t o many p e a k s ^ n .m.r. s p e c t r u m a n a l y s i s a l s o s h o w e d t h a t a m i x t u r e o f t r i m e t h y l t i n h y d r i d e a n d p e r f l u o r o c y c l o b u t e n e w a s o n l y 0.13% r e a c -t e d a f t e r 30 m i n u t e s . T h e e y e l o b u t y l t r i m e t h y I t i n ( 1 . 0 2 5 g) w a s v a c u u m s e a l e d a n d l e f t a t 20° f o r 10 d a y s . P e n t a f l u o r o c y c l o b u t e n e ( 0 . 2 Q"g) w a s p r o d u c e d a n d i d e n t i f i e d b y i t s m o l e c u l a r w e i g h t o f 144 ( m a s s s p e c . ) a n d 142 ( v a p o u r ) ( C a l c : 144)• U n d e c o m p o s e d l , 2 , 3 , 3 5 4 > 4 ~ h e x a -f l u o r o c y c l o b u t y l t r i m e t h y l t i n ( 0 . 5 5 7 g) w a s r e c o v e r e d . T h e r e m a i n -i n g i n v o l a t i l e . s o 1 i d w a s i d e n t i f i e d a s t r i m e t h y l t i n f l u o r i d e , m.p. >320° ( l i t . v a l u e d e c o m p o s e s > 3 6 0 ° ) ( F o u n d : C, 2 0 . 0 ; H, 5 . 0 % . C a l c . f o r C . H q F S n : C, 19-7; H, 4-9 %) . 52 ( f ) R e a c t i o n o f T r i e t h y l t i n H y d r i d e a n d P e r f l u o r o c y c l o b u t e n e - - T r i e t h y l t i n h y d r i d e ( 8 . 1 g) a n d t h e c y c l o b u t e n e ( l k . 5 g) w e r e l e f t a t 20° f o r 2 m o n t h s . T h e s o l u t i o n w e n t c l o u d y i m m e d i a t e l y a n d a f t e r o n e d a y t h e r e Was c o n s i d e r a b l e p r e c i p i t a t e . T h e f r a c -. . . o t i o n ( I 3 . 4 g) W h i c h w e n t t h r o u g h a -23 b a t h c o u l d n o t be s e p a r -a t e d a n y f u r t h e r b y t r a p - t o - t r a p d i s t i l l a t i o n a n d i t s i n f r a r e d s p e c t r u m s h o w e d t w o a b s o r p t i o n s i n t h e d o u b l e b o n d r e g i o n a t 5-°/££ ( C F = C F C F 2 C F 2 ) a n d 5 - 9 / 7 - A s e c o n d f r a c t i o n ( O . k g) w h i c h c o n d e n -s e d i n a - 2 3 ° t r a p w a s i d e n t i f i e d a s 1 , 2 , 3 , 3 > W h e x a f l u o r o c y c l o -b u t y l t r i e t h y l t i n b y i n f r a r e d a n a l y s i s a n d h a d d e c o m p o s e d c o m p l e t e l y w i t h i n , o n e w e e k t o t r i e t h y l t i n f l u o r i d e , m.p. 2 5 5 - 2 5 7 ° ( a s a m p l e p r e p a r e d f r o m t r i e t h y l t i n c h l o r i d e i n a q u e o u s K F a n d r e c r y s t a l -l i z e d f r o m e t h a n o l g a v e t h e same m e l t i n g p o i n t ) ( F o u n d : C, 3 2 . 0 ; H, 5 - 9 %. C a l c . f o r C ^ H ^ F S n : C, 3 2 . 7 ; H,. 6 . 7 %) . T r i e t h y l t i n f l u o r i d e ( 8 . 8 g) w a s r e c o v e r e d f r o m t h e o r i g i n a l r e a c t i o n . ( g ) . R e a c t i o n o f T r i e t h y l t i n H y d r i d e a n d 1 , 2 - D i c h l o r o t e t r a -f l u o r o c y c l o b u t e n e  T r i e t h y l t i n h y d r i d e ( 2 . 9 g) a n d t h e c y c l o b u t e n e ( 1 1 . 0 g) w e r e h e a t e d a t 100° f o r o n e d a y . T h e v o l a t i l e f r a c t i o n ( 1 0 . 9 g) c o n -t a i n e d n o t r i e t h y l t i n g r o u p a n d h a d t w o i n f r a r e d a b s o r p t i o n s i n t h e d o u b l e b o n d r e g i o n a t 6. lyU (CC 1 = C C l c l ^ C F ^ a n d 6 . 3 ^ . . T h e i n v o l a t i l e f r a c t i o n w a s i d e n t i f i e d a s t r i e t h y l t i n c h l o r i d e (3-1 9, 91%) b y i t s k n o w n i n f r a r e d s p e c t r u m a n d v . p . c . a n a l y s i s ( 5 ' U c o n P o l a r a t 175°) w i t h a r e t e n t i o n t i m e o f 2 3 ' m i n . 15 s e c . ( ( C 2 H ^ ) ^ S n C 1 : 23 m i n . L0 s e c . ) . . , • ' ( h ) R e a c t i o n o f T r i e t h y l t i n H y d r i d e a n d 1 , 2 - D i c h l o r o h e x a f l u o r -ocy.c l o p e n t e n e  T r i e t h y l t i n h y d r i d e ( 3 - 4 g) a n d t h e e y e L o p e n t e n e (12.5 g) w e r e h e a t e d a t 100° f o r o n e d a y . T r i e t h y l t i n c h l o r i d e (3-7 g> 93%) w a s p r o d u c e d a s i d e n t i f i e d b y i t s i n f r a r e d , s p e c t r u m . T h e v . p . c . a n a l -y s i s s h o w e d o n l y o n e c o m p o n e n t ( 5 1 U c o n P o l a r a t 1 9 0 ° ) . 53 D I S C U S S I O N A . A r s i n e s (1) R e s u l t s I n t h e p r e s e n t i n v e s t i g a t i o n I t was f o u n d t h a t t h e r e a c t i o n o f a r s i n e s w i t h f l u o r o c y c l o b u t e n e s a n d f l u o r o c y c l o p e n t e n e s c a n be r e p r e s e n t e d by t h e g e n e r a l e q u a t i o n : R 2 A s H + C X = C X , ( C F 2 ) n * R 2 A s C = C X ( C F 2 ) n + HX X = C I , . F ; n = 2, 3 T h u s d i m e t h y l a r s i n e a n d 1 , 2 - d i c h l o r o t e t r a f l u o r o c y c l o b u t e n e a f -f o r d l - c h l o r o - 2 - d i m e t h y l a r s i n o t e t r a f l u o r o c y c 1 o b u t e n e a n d h y d r o -g e n c h l o r i d e b o t h i n q u a n t i t a t i v e y i e l d a t 1 0 0 ° . ( C H 3 ) 2 A s H + C C 1 = C C 1 C F 2 C F 2 » (CH^) ^ s t ^ C C 1 C F 2 C F 2 + HC1 T h i s r e a c t i o n p r o d u c t i s i d e n t i c a l w i t h t h a t f r o m c a c o d y l a n d 1 ,2-98 d i c h l o r o c y c l o b u t e n e i . ( C H 3 ) ^ A s 2 •+ C C 1 = C C 1 C F 2 C F 2 • (CH^) g A s ^ C C 1 C F 2 C F 2 + ( C H ^ J g A s C l T h e r e a c t i o n o f d i m e t h y l a r s i n e w i t h 1 , 2 - d i c h l o r o h e x a f l u o r o -c y c l o p e n t e n e "to g i v e t h e e x p e c t e d p r o d u c t , 1 - c h l o r o - 2 - d i m e t h y 1 -a r s i n o h e x a f 1 u o r o c y c l ' o p e n t e h e , i s 55% c o m p l e t e a f t e r t w o d a y s a t 1 0 0 ° . , . , ( C H 3 ) 2 A s H + C C 1 = C C 1 C F 2 C F 2 C F 2 • ( C H ^ ) 2 A s t = C C ' 1 G F 2 C F 2 C F 2 +' HC1 A s i n t h e c a s e o f t h e e y e l o b u t e n e ' , d e r i v a t i v e . ? t h i s same a r s i n o -c y c l o p e n t e n e h a s a l s o b e e n o b t a i n e d by t h e r e a c t i o n o f c a c o d y l 98 a n d 1 y 2 - d i c h l o r o h e x a f l u o r o c y c l o p e n t - e n e ( C H 3 ) i + A s 2 + C C 1 = C C 1 C F 2 C F 2 C F 2 ( C H ^ ) 2 A s C = C C 1 C F 2 C F 2 C F 2 + ( C H ^ ) ^ s C 1 A s t u d y was made o f t h e r a t e s o f r e a c t i o n o f d i m e t h y l a r s i n e w i t h C X = C X C F 2 C F 2 ( X = C 1 , F ) by m i x i n g t h e r e a c t a n t s i n a n n . m . r . t u b e . T h e 1 - d i m e t h y l a r s i h o p e n t a f l u o r o c y c l o b u t e n e h a s p r e v i o u s l y b e e n q u a n t i t a t i v e l y o b t a i n e d by t h e r e a c t i o n o f d i m e t h y l a r s i n e a n d p e r f 1 u o r o c y c l o b u t e n e a f t e r s e v e n d a y s a t 20° . 51+ (CH^-AsH + 6 F = C F C F 2 C F-; • (CH^) 2As6=CFCF 2CF 2 + HF It was found that the r e a c t i o n w i t h . p e r f l u o r o c y c l o b u t e n e i s con-s i d e r a b l y f a s t e r at 2 0 ° than the r e a c t i o n w i t h 1 , 2 - d i c h l o r o t e t r a -f l u o r o c y c l o b u t e n e . Thus, whereas the former r e a c t i o n i s 35% comp-l e t e a f t e r one day and 85% complete a f t e r four days, the l a t t e r r e a c t i o n i s only 35% complete a f t e r twelve days. Under more f o r c i n g c o n d i t i o n s ( l_j.0°) a second mole of d i -methy l a r s i n e r e a c t s with l - c h l o r o - 2 - d i m e t h y l a r s i n o t e t r a f l u o r o cyclobutene to give the 1 , 2 - b i s ( d i m e t h y l a r s i n o ) e y e l o b u t e n e der-i v a t i v e , b.p. 120° (1+7 mm) . (CH 3)pAsH +. ( C H 3 ) 2AsC=CC 1 C F 2 C F 2 * (CH^) 2AsC=C(As(CH^) ^ C F ^ C F g + HCl The product, 1 , 2 - b i s ( d i m e t h y l a r s i n o ) t e t r a f l u o r o c y c l o b u t e n e , i s i d e n t i f i e d by m i c r o a n a l y s i s . a n d molecular weight. The a r s i n e r gives only a very weak a b s o r p t i o n at &.2yi( in, the double bond r e g i o n of the spectrum. On the b a s i s of t h i s weak i n f r a r e d ab-s o r p t i o n the symmetrical 1 , 2 - b i s ( d i m e t h y l a r s i n o ) d e r i v a t i v e i s favoured over the 1,3" Q r 1 ,l+-bi s( dimethy l a r s i n o ) d e r i v a t i v e s s i n c e these l a t t e r two compounds would be expected to have a strong i n f r a r e d a b s o r p t i o n i n the double bond r e g i o n s i m i l a r to 98 l - c h l o r o - 2 - d i m e t h y l a r s i n o t e t r a f l u o r o c y c l o b u t e n e . An i n t e r e s t i n g r e s u l t of t h i s r e a c t i o n i s the low y i e l d of b i s ( d i m e t h y l a r s i n e ) d e r i v a t i v e {$2% based,on d i m e t h y l a r s i n e ) and the o v e r a l l 2 : 1 . 2 , dimethy l a r s i n e - d i m e t h y l a r s i n o c y c lobutene, stoch'iometry of the r e a c t i o n . A f t e r t a k i n g i n t o account the y i e l d of the b i s ( d i -m e t h y l a r s i n o ) c y c l o b u t e n e the remaining m a t e r i a l i s approximately four p a r t s d i m e t h y l a r s i n e to one p a r t d i m e t h y l a r s i n o c y c l o b u t e n e . It thus appears that the a l l y l i c f l u o r i n e s are atta c k e d and from 89 the r e s u l t s of Park and coworkers , who found that a l c o h o l s a t t a c k 55 the a l l y l i c f l u o r i n e s of l - a l k o x y - 2 - c h l o r o t e t r a f l u o r o c y c l o b u t e n e t o form a t r i a l k o x y ROH f R 0 C = C C 1 C F 2 C F 2 — R O C = C C I C ( O R ) 2 C F 2 d e r i v a t i v e , the f o l l o w i n g r e a c t i o n i s p o s t u l a t e d as a p o s s i b l e s i d e r e a c t i o n . 2 ( C H 3 ) _ A s H + ( C H 3 ) p A s C = C ( A s ( C H ^ ) 2 ) C F 2 C F 2 • ( C H 3 ) 2 A s C = C ( A s ( C H 3 ) 2 ) G F 2 C ( A s ( C H 3 ) 2 ) 2 + 2 H C 1 No r e a c t i o n o c c u r s between m e t h y l p h e n y l a r s i n e and p e r f l u o r o -o c y c l o b u t e n e a f t e r one day a t 2 0 , and the r e a c t i o n i s o n l y 3 0 - 5 0 % complete a f t e r s eventeen hours a t 100°. (C 6H^)CH-AsH+ CF=CFCF 2CF 2 * ( C ^ ) C H 3 A s C = C F C F 2 C F 2 + HF The r e a c t i o n p r o d u c t , 1 - m e t h y l p h e r t y l a r s i n o p e n t a f l u o r o c y c l o b u t e n e , b.p. 10k° ( 1 5 mm), i s i d e n t i f i e d by i t s ^ F n.m.r. spectrum w h i c h shows peaks a t 27.5» 33'7 and 39.7 p.p.m. ( r e l a t i v e i n t e n s i t y 1 : 2 : 2 ) . T h i s i s i n agreement w i t h the *9F n.m.r. spectrum o f (CH^) 2AsC=CFCF 2CF 2 which shows peaks at 28 . 9 , 33-7 and 39-4 p.p.m. ( r e l a t i v e i n t e n s i t y 1 : 2 : 2 ) * ^ . The m e t h y l p h e n y l a r s i n o d e r i v a t i v e has a s t r o n g a b s o r p t i o n i n i t s i n f r a r e d spectrum a t 1659 cm 1 which i s a s s i g n e d t o t h e double bond. T h i s compares f a v o u r a b l y , w i t h a s t r o n g a b s o r p t i o n a t 1695 cm * f o r 1 - d i m e t h y l a r s i n o p e n t a -f l u o r o c y c l o b u t e n e ^ - 1 . At 100° the r e a c t i o n o f d i m e t h y l a r s i n e w i t h the n o n - c y c l i c f l u o r o o l e f i n , h e x a f l u o r o p r o p e n e , g i v e s a q u a n t i t a t i v e y i e l d o f the a d d i t i o n p r o d u c t , 2 - H - 2 - d i m e t h y l a r s i n o h e x a f l u o r o p r o p a n e , b.p. 110° ( 7 3 9 mm). (CH^igAsH + CF 2=CFCF 3 * (CH 3) ^sCFpCFHCF-j The i n f r a r e d spectrum o f t h i s r e a c t i o n p r o d u c t shows no i n d i c a t i o n o f a double bond. Even upon h e a t i n g t o l80° t h i s 1:1 adduct was s t a b l e , t h e s t r u c t u r e o f the a r s i n e i s v e r i f i e d by i t s r e a c t i o n £6 w i t h e x c e s s b r o m i n e t o a f f o r d 2 - H - 1 - b r o m o h e x a f l u o r o p r o p a n e a n d m e t h y l b r o m i d e . ( C H 3 ) 2 A s C F 2 C F H C F 3 + B r 2 • C H ^ B r + C F ^ r C H F C F - j ( 2 ) P r o p o s e d M e c h a n i s m s M i l l e r a n d c o w o r k e r s 1 ^ 1 p o s t u l a t e d t h e f o l l o w i n g m e c h a n i s m f o r m e t h o x y a d d i t i o n t o , f l u o r o e t h y l e ' n e s . F F n - \ • t r a t e \ (~' - CH.O + C-C 1 , i • * C H o 0 - C - C -3 / \ c o n t r o l l i n g 3 / ^ C H OH + CH^O-C-C- f a s t > CH-O-C-C- + C H „ 0 ~ 3 3 i A 3 / \ 3 A s i m i l a r m e c h a n i s m i s f a v o u r e d a s t h e r a t e d e t e r m i n i n g s t e p f o r r e a c t i o n o f a r s i n e s w i t h f l u o r o c y c l o o l e f i n s , e . g . ( C H ^ ^ s H + C 1 C = C C 1 C F 2 C F 2 = * Cl^F © X-CGCFZCFZ ( C ^ A s H , . T h i s c o u l d b-e f o l l o w e d b y i n t r a m o l e c u l a r A s - H c l e a v a g e t o f o r m t h e a d d i t i o n p r o d u c t , ( C H ^ ) ^ s C C l C C l H C F ^ C F ^ f o l l o w e d b y r a p i d e l i m i n a t i o n o f h y d r o g e n c h l o r i d e . ( C H 3 ) 2 A s C C l C C l H C F 2 C F 2 * ( C H 3 ) 2 A s C = C C 1 C F 2 C F 2 + H C l T h u s , t h e f a s t e r r e a c t i o n o f d i m e t h y l a r s i n e w i t h p e r f l u o r o c y c l o -b u t e n e c o m p a r e d w i t h 1 , 2 - i d i c h l o r o t e t r a f l u o r o c y c l o b u t e n e c a n he e x p l a i n e d b y i n d u c t i v e e f f e c t s , t h e f l u o r i n e h a v i n g g r e a t e r e l e c - -t r o n w i t h d r a w i n g p o w e r t h a n t h e c h l o r i n e a n d l e a v i n g t h e v i n y l l i c c a r b o n m o r e s u s c e p t i b l e t o n u c l e o p h i l i c a t t a c k . A l s o t h e r e l -a t i v e l y s l o w r e a c t i o n o f m e t h y l p h e n y l a r s i n e - . w i t h p e r f l u o r o c y c l o -b u t e n e c a n b e e x p l a i n e d b y t h e d e c r e a s e i n a v a i l a b i 1 i t y o f t h e a r s e n i c l o n e p a i r d u e t o t h e i n d u c t i v e a n d p o s s i b l e r e s o n a n c e e f f e c t s o f t h e p h e n y l . g r o u p , t h u s m a k i n g m e t h y l p h e n y l a r s i n e a w e a k e r n u c l e o p h i l e t h a n d i m e t h y l a r s i n e . T h i s p r o p o s e d m e c h a n i s m i n v o l v i n g a d d i t i o n f o l l o w e d b y e l -57 i m i n a t i o n i s analogous t o t h e mechanism p o s t u l a t e d f o r the r e a c -9 k 8k t i o n of p e r f l u o r o c y c l o b u t e n e w i t h amines , G r i g n a r d r e a g e n t s , 87 92 a l c o h o l s and t h i o l s , e.g. CF=CFCF 2CF 2 + RMgX XMgCFCF(R)CF 2CF 2j CF= c'(R)CF 2CF 2 + MgXF 8k However, a l t h o u g h Park and F o n t a n e l l i f a v o u r a d d i t i o n f o l l o w e d by e l i m i n a t i o n f o r the r e a c t i o n o f G r i g n a r d r e a g e n t s w i t h p e r f l u o r -86,89 ocyc1obutene, Park and coworkers ' have p o s t u l a t e d a s u b s t i t u t i o n mechanism f o r the base c a t a l y z e d r e a c t i o n of a l c o h o l s w i t h p e r -f l u o r o c y c l o b u t e n e e i t h e r by d i r e c t ' s u b s t i t u t i o n (S^2) a t the v i n y l i c p o s i t i o n or s u b s t i t u t i o n at an a l l y l i c p o s i t i o n f o l l o w e d by rearr-angement . ROH + C~F=CFCF 2CF 2 N a 0 H .. (RO)CFCF 2CF=CF + NaF +. H 2 0 (RO)CFCF 2CF=CF » (RO)C=CFCF 2CF 2 P o s s i b l y the b e s t c o r r o b o r a t i n g e v i d e n c e i s the a d d i t i o n of a second mole of t h i o l " t o the 1 - m e r c a p t o p e n t a f l u o r o c y c l o b u t e n e t o 92 g i v e a 1 , 2 - d i m e r c a p t o c y c l o b u t a n e RSH + RS6'=CFCF2CF2 * RSCHCF ( SR) C F 2 C F 2 T h i s a d d i t i o n p r o d u c t decomposed on d i s t i l l a t i o n t o g i v e hydrogen f l u o r i d e and the butene d e r i v a t i v e . RSCHCF ( S R ) C F 2 C F 2 » Rs6=C( SR)"CF~CF + HF The e x i s t e n c e of any a p p r e c i a b l e c o n c e n t r a t i o n of a d d i t i o n p r o d -u c t from the e y e l o b u t t n e - a r s i n e r e a c t i o n s does not occur as t e s t -i f i e d by the absence of any measurable CHF or CHC1 p r o t o n i n the *H n.m.r. s p e c t r a of the r e s p e c t i v e e y e l o b u t e n e - a r s i n e m i x t u r e s . 101 102 92 The r e a c t i o n of a l c o h o l s , amines and t h i o l s w i t h n o n - c y c l i c f l u o r i n a t e d e t h y l e n e s g i v e s the 1:1 a d d i t i o n p r o d u c t s , e.g. C 2H^SH + CF 2CFC1 • C 2H^SCF 2CFC1H In t h i s i n v e s t i g a t i o n the a d d i t i o n of d i m e t h y l a r s i n e to h e x a f l u o r -58 o p r o p e n e a l s o o n l y g i v e s t h e 1:1 a d d u c t a n d e v e n a f t e r h e a t i n g a t l 8 0 ° f o r t w e n t y - o n e h o u r s t h e r e i s no s i g n o f h y d r o g e n f l u o r i d e o r t h e p r o p e n e d e r i v a t i v e . T h i s i s c o r r o b o r a t e d b y t h e r m o -15 c h e m i c a l d a t a c o n c e r n i n g t h e c h l o r i n a t i o n o f f l u o r o b ' l e f i n s . T h e e n t h a l p y o f c h l o r i n a t i o n o f p e r f l u o r o c y c l o b u t e n e i s 20 k c a l / m o l e m o r e t h a n f o r p e r f l u o r o e t h y l e n e a n d 10 k c a l / m o l e m o r e t h a n f o r p e r f l u o r o p r o p e n e . B . G r o u p I V H y d r i d e s ( 1) R e s u l t s T h e r e a c t i o n o f t r i m e t h y 1 - s i l a n e , - g e r m a n e , a n d - t i n h y d r i d e w i t h p e r f l u o r o c y c l o b u t e n e c a n be r e p r e s e n t e d by t h e f o l l o w i n g e q u a t i o n . ( C H 3 ) 3 M H + C F = C F C F 2 C F 2 *• ( C H 3 ) 3 M C F C F H C F 2 C F 2 M - S i , G e , S n T h u s p e r f l u o r o c y c l o t i u t e n e a n d t r i m e t h y l g e r m a n e g i v e t h e a d d i t i o n p r o d u c t , 1 - H - h e x a f l u o r o c y c l o b u t y l - 2 - t r i m e t h y l g e r m a n e , b . p . 1 1 8 ° (752 mm), i n q u a n t i t a t i v e y i e l d a f t e r t h r e e d a y s a t 2 3 0 ° . ( C H - J ^ G e H + C F = C F C F 2 C F 2 — — - (CH^) ^GeCF^CFp H C F _ C F 2 . T h e i n f r a r e d s p e c t r u m o f t h i s a d d i t i o n p r o d u c t s h o w s n o a b s o r p -t i o n i n t h e d o u b l e b o n d r e g i o n a n d s h o w s s t r o n g C'F a b s o r p t i o n s a t 1398, 133-|., 12-4.1 a n d 1185 c m - 1 . T h e s t r u c t u r e i s b e s t s h o w n b y t h e , n . m . r . s p e c t r u m w h i c h s h o w s t w o a b s o r p t i o n s , a s i n g l e m e t h y l p e a k a t - 0 . 2 5 p . p . m . a n d t h e m e t h i n e m u l t i p l e t a t - 5 - 0 1 p . p . m . w i t h J „ „ =55 c p s a n d J u r • = 22 c p s , o f r e l a t i v e i n t e n s i t y 1 : 9 . 3 « . T h e s i n g l e m e t h y l a b s o r p t i o n . a n d ' t h e m e t h i n e m u l t i p l e t i n d i c a t e t h a t t h e r e i s o n l y one i s o m e r p r e s e n t . T h e c o n - f i g u r -a t i o n a n d c o n f o r m a t i o n o f t h i s i s o m e r a n d i t s * H n . m . r . s p e c t r u m a r e - d i s c u s s e d i n d e t a i l o n p a g e 7 1 . T a b l e I V g i v e s a l i s t o f t h e h e x a f l u o r o c y c l o b u t y l d e r i v a t i v e s 59 p r e p a r e d i n t h i s i n v e s t i g a t i o n w i t h t h e r e a c t i o n c o n d i t i o n s u n d e r w h i c h t h e y w e r e f o r m e d a n d t h e i r r e s p e c t i v e y i e l d s . T h e i r b o i l i n g p o i n t s , p e r t i n e n t *H n.m.r. d a t a a n d t h e i n f r a r e d a b s o r p t i o n b a n d s i n t h e C F s t r e t c h i n g r e g i o n a r e a l s o g i v e n . T h e s i m i l a r i t y o f t h e i r s p e c t r a i s r e a d i l y a p p a r e n t . T h e a d d i t i o n p r o d u c t f r o m t h e t r i m e t h y l s i l a n e - p e r f l u o r o c y c l o -b u t e n e r e a c t i o n c o u l d n o t be a n a l y z e d , b e i n g v e r y s e n s i t i v e t o a i r . H o w e v e r m o l e c u l a r w e i g h t m e a s u r e m e n t s i n d i c a t e d p u r i t y o f t h e a d d i t i o n p r o d u c t a n d t h e i n f r a r e d a n d *H n.m.r. s p e c t r a c o n -f i r m i t s s t r u c t u r e ( s e e T a b l e I V ) . 1 • T A B L E I V D A T A C O N C E R N I N G H E X A F L U O R O B U T Y L D E R I V A T I V E S R 3 M C F — C F H (1) R e a c t i o n C o n d i t i o n s o f F o r m a t i o n , b . p . , a n d some *H n . m . r . d a t a C o m p o u n d ,Rx. R x . Y i e l d b . p . JHF* JHFe (p-p-m-) R M Temp. T i m e ( c p s ) m e t h i n e C H ^ S i 250° k d a y s ~60% 1 1 2 ° (756 mm) 22 52 - 4 . 9 3 C H Ge 3 230° 3 d a y s 100% 1 1 8 ° (752 mm) 22 55 - 5 . 0 1 C H ^ S n 20° k d a y s 92% d e c o m p o s e s 22.5 55 - 5 . 1 0 C £ H ^ S n 20° 60 d a y s 3% d e c o m p o s e s - -(2) I n f r a r e d S p e c t r a a ( P r i n c i p a l A b s o r p t i o n s ) R,M C H 3 , S i ' C H 3 , Ge C H 3 , S n C 2 H ^ , S n a ' C 1398 s 1333 s 1281 m 12k0 v s 1177 v s 1037 s 1001 s 956 v s L i q u i d f i l m 1398 s 1334 s 1282 m 1 2 k l v s 1185 v s 1035 s 1003 s 959 v s 1390 s 1329 s 1273 m 1235 v s 1172 v s 1018 s : 999 s 9k9 v s 1390 s 1330 s 1275 m 1235 s 1170 v s 1020 s 1000 s 950 v s V a p o u r A p p r o x i m a t e ( v a l u e s t a k e n f r o m P E 137) 60 T h e a d d i t i o n p r o d u c t f r o m t r i m e t h y l t i n h y d r i d e a n d p e r f l u o r o -c y c l o b u t e n e i s o b t a i n e d i n 92% y i e l d a f t e r f o u r d a y s a t 20° w i t h t h e r e m a i n i n g , t i n b e i n g p r e s e n t a s t r i m e t h y l t i n f l u o r i d e . T h e s t r u c t u r e o f t h i s 1:1 a d d u c t i s a g a i n b e s t , s h o w n b y i t s * H n . m . r . s p e c t r u m o f a m e t h y l a b s o r p t i o n ( s i n g l e t ) a t - 0 . 2 8 p . p . m . a n d a m u l t i p l e t a t -5.10 p . p . m . T a b l e I V s h o w s t h a t t h e i n f r a r e d s p e c -t r u m i s v e r y s i m i l a r t o i t s s i l i c o n a n d g e r m a n i u m a n a l o g u e s . T h e a d d i t i o n r e a c t i o n i s s l o w a t 20° b e i n g a p p r o x i m a t e l y 3>% c o m p l e t e o a f t e r t h i r t y m i n u t e s . T h e a d d i t i o n p r o d u c t i s u n s t a b l e a t 20 d e c o m p o s i n g . t o t r i m e t h y l t i n f l u o r i d e a n d 1 - H - p e n t a f l u o r o c y c l o b u t -e n e . T h e d e c o m p q s i t i o n (CH^) ^ . S n C F C F H C F ^ C F - — — C H = C F C F 2 C F 2 + ( C H ^ S n F i s a b o u t L|.6% c o m p l e t e a f t e r t e n d a y s . T h e p e n t a f l u o r o c y c l o b u t e n e i s i d e n t i f i e d by i t s m o l e c u l a r w e i g h t ( v a p o u r a n d m a s s s p e c t r o m -e t e r ) a n d i n f r a r e d s p e c t r u m w h i c h s h o w s a d o u b l e b o n d a b s o r p t i o n a t S'9/U.y C - H s t r e t c h a t 3 . 1 / ^ a n d = C - H o u t o f p l a n e b e n d i n g a t l l . l y C L . T h e a b s e n c e o f 1 , 2 , 3 , k , k - p e n t a f l u o r o c y c l o b u t - 1-ene i s c o n s i s t e n t w i t h t h e r e s u l t s o b t a i n e d f o r t h e d e h y d r o f l u o r i n a t i o n o f l , 2 , 3 , 3 j k , k - h e x a f l u o r o c y c l o b u t a n e , 1 uryu r \ C F H C F H C F 0 C F 0 — ^ * CF=CHCF_CF„ + HF 2 2 ROH 2 2 T h e r e a c t i o n o f p>erf l u o r o c y c l o b u t e n e a n d t r i e t h y l t i n h y d r i d e o a f t e r t w o m o n t h s a t 20 g i v e s o n l y a 3% y i e l d o f t h e a d d i t i o n p r o d -u c t w h i c h c a n be i d e n t i f i e d by i t s . i n f r a r e d s p e c t r u m ( s e e T a b l e I V ) T h e r e m a i n i n g t i n i s p r e s e n t a s t r i e t h y l t i n f l u o r i d e . T h u s , l i k e t h e t r i m e t h y l t i n - p e r f l u o r o c y c l o b u t e n e a d d u c t , t h e t r i e t h y l t i n a d -d u c t i s u n s t a b l e w i t h r e s p e c t t o e l i m i n a t i o n o f t i n f l u o r i d e . T h e p r o d u c t s f r o m t h e r e a c t i o n s o f G r o u p I V h y d r i d e s w i t h 1 , 2 - d i c h l o r o t e t r a f l u o r o c y c l o b u t e n e v a r y c o n s i d e r a b l y w i t h v a r -i a t i o n s i n t h e G r o u p I V e l e m e n t . T h e s l o w r e a c t i o n o f t r i m e t h y l -61 s i l a n e w i t h 1 , 2 - d i c h l o r o t e t r a f l u o r o c y c l o b u t e n e s t i l l g i v e s a t r a c e of u n r e a c t e d t r i m e t h y l s i l a n e a f t e r t w e l v e hours a t 1 9 0 ° . There a r e two major r e a c t i o n p r o d u c t s , 1 - c h l o r o t e t r a f l u o r o c y c l o -b u t e n y 1 - 2 - t r i m e t h y l s i l a n e ( 6 0 % ) , b.p. 132° (762 mm), and c h l o r o -t r i m e t h y l s i l a n e (38%) and two minor p r o d u c t s , hydrogen c h l o r i d e and l - H - 2 - c h l o r o t e t r a f l u o r o c y c l o b u t e n e . ( C H - ^ S i H + C C 1 = C C 1 C F 2 C F 2 • (CH^) ^ S i ^ C C l C F ^ c h ^ + HCl + ( C H - ^ S i C l + C H = C C 1 C F 2 C F 2 The b u t e n y l t r i m e t h y l s i l a n e has a s t r o n g a b s o r p t i o n i n i t s i n f r a - 1 r e d spectrum, at 1576 cm"' w h i c h - i s a s s i g n e d t o the double bond. The i n f r a r e d spectrum of the f r a c t i o n c o n t a i n i n g u n r e a c t e d 1 ,2-d i c h l o r o t e t r a f l u o r o c y c l o b u t e n e shows two a b s o r p t i o n s i n the double bond r e g i o n , the one a t 6. "i^U b e i n g a t t r i b u t e d t o l - H - 2 - c h l o r o t e t -80 r a f l u o r o c y c l o b u t e n e The r e a c t i o n between t r i m e t h y l g e r m a n e and 1 , 2 - d i c h l o r o t e t r a -f l u o r o c y c l o b u t e n e g i v e s a r e l a t i v e l y l a r g e number o f p r o d u c t s . o The r e a c t i o n i s 20% complete a f t e r t h i r t y - s i x - h o u r s a t 190 . V. p . c . a n a l y s i s o f the r e a c t i o n p r o d u c t s shows the p r e s e n c e o f s i x ger-manium compounds. C F , - C £ (CH3)3GeH + J C | J , C ) • tH 3) 3GeCI (I) cL ^ - p i ( r I ) > C i - f l ( l u ) (CH 3 ; 3 G e C = £ H (cH 3) 3GeC=CCf ( C ^ G e C H - C H C ! (CH^GeCCI-CHCI The major component (36 mole %) i s 1 - c h l o r o t e t r a f l u o r o c y c l o b u t -e n y l t r i m e t h y l g e r m a e ( I I I ) , b.p. 7 8 ° (50 mm) whi c h i s i d e n t i f i e d 62 by a n a l y s i s , by i t s *H n.m.r. spectrum of only one sharp peak at - 0 . 2 1 p.p.m. and by the strong double bond i n f r a r e d a b s o r p t i o n at 1576 cm * which occurs at the same frequency as that of analogous s i l a n e d e r i v a t i v e . Chlorotrimethylgermane (I) (32 mole %) i s the second l a r g e s t component. The l e a s t v o l a t i l e component (21%) i s i d e n t i f i e d as 1 , 2-di-c h l o r o - 3 , 3 , k , k - t e t r a f luorocyc l o b u t y l t r imethy lgermane (VI) , b.p. 86° (50 mm), by i t s *H n.m.r. spectrum of a s i n g l e t at -O.I4.9 p.p.m. (-CH^) and a septet at -k . 5 k p.p.m. ( r e l a t i v e i n t e n s i t y 1 : 9 . 2 ) . The *H n.m.r. spectrum of t h i s molecule i s d i s c u s s e d i n d e t a i l on page 6k (see F i g u r e 2) . Two minor peaks ( 3 - 5 and 7%) are i d e n t i f i e d as c i s and t r a n s i somers of l - c h l o r o - 3 , 3 , k , k - t e t r a f l u o r o c y c 1 o b u t y 1 - 2 - t r imethy l g e r -mane (IV, V) by t h e i r *H n.m.r. s p e c t r a . The *H n.m.r. spectrum of the t r a n s isomer, which was analyzed, shows a methyl absorp-t i o n at - 0 . 2 9 p.p.m. (s i r n g l e t ) and unresolved m u l t i p l e t s at - 2 . 5 7 and -k . 5 6 p.p.m. ( r e l a t i v e i n t e n s i t y 9 . 0 : 1 . 0 : 0 . 9 ) which are as-signed to the methine a b s o r p t i o n s . It i s assigned the t r a n s con-f i g u r a t i o n because of the broadness of the methine m u l t i p l e t s , i . e . J ^ t r a n s ^ J c i s . Again the *H n.m.r. s p e c t r a of these isomers are d i s c u s s e d i n more d e t a i l on page 6 8 . The H n.m.r. s p e c t r a assigned to the c i s isomer shows a methyl a b s o r p t i o n at - 0 . 3 1 p.pjn. and methine a b s o r p t i o n s at - 2 . 3 and -i+.05 p.p.m. ( r e l a t i v e i n t e n -s i t y 9 . 0 : 0 . 9 : 1 . 0 ) . The s m a l l e s t component (0.5%) i s i d e n t i f i e d as 1 - H - t e t r a f l u o r -o c y c l o b u t e n y l - 2 - t r i m e t h y l g e r m a n e (II) by i t s i n f r a r e d and *H n.m.r. s p e c t r a . I t s i n f r a r e d spectrum shows no double bond a b s o r p t i o n , however, l - H - 2 - d i m e t h y l a r s i n o t e t r a f l u o r o c y c l o b u t e n e shows only a weak a b s o r p t i o n at 1545 cm 1 *00^ strong to very strong 63 C-F s t r e t c h i n g a b s o r p t i o n s i n the i n f r a r e d spectrum of the germane occur at 1333» 1261, 1168 and .1117 cm * and are i n very good ag-reement wi t h those of the a r s i n e which occur at 1330, 1265, 1160 and 110k cm The n.m.r. spectrum of the germane shows a methyl a b s o r p t i o n at - 0 . 3 3 p.p.m. and a methine a b s o r p t i o n , a t r i p l e t , at - 6 . 7 9 p.p.m. (J = 9 - 5 c p s ) . T h i s agrees with the H n.m.r. spectrum of the a r s i n o d e r i v a t i v e where the methine ab-s o r p t i o n at - 6 . 8 0 p.p.m. i s a l s o a t r i p l e t (J = 10 cps) When trimethylgermane and 1 , 2 - d i c h l o r o c y c l o b u t e n e are heated at 230° f o r three days, no t r a c e of trimethylgermane remains. Hy-drogen c h l o r i d e i s recovered as a r e a c t i o n product. V.p.c. a n a l -y s i s of the r e a c t i o n products shows only f i v e germanium' compon-ents with no t r a c e of 1 , 2 - d i c h l o r o - 3 , 3 j k , k - t e t r a f luorocyc l o b u t -y l t r i m e t h y l g e r m a n e (VI) and a n i n e - f o l d i n c r e a s e i n the 1-H-tet-r a f l u o r o c y c l o b u t e n y 1 - 2 - t r i m e t h y l g e r m a n e (II) (5 mole %) . The r e a c t i o n of t r i e t h y l t i n h y dride with 1 , 2 - d i c h l o r o t e t r a -o f l u o r o c y c l o b u t e n e and 1 , 2 - d i c h l o r o h e x a f l u o r o c y c l o p e n t e n e at 100 g i v e s q u a n t i t a t i v e y i e l d s of t r i e t h y l t i n c h l o r i d e . ( G 2 H 5 ^ 3 S n H + C 1 C = C C 1 ( G F 2 ) n — ( C 2 H ^ ) 3 S n C l + C C l = C H ( C F 2 ) n n = 2 , 3 The v o l a t i l e f r a c t i o n from the cyclobutene r e a c t i o n shows two ab-s o r p t i o n s i n the double bond r e g i o n of the i n f r a r e d s p e c t r a which are assigned to the 1-H-cyclobutene and 1 , 2 - d i c h l o r o c y c l o b u t e n e . , s 1 (2) H N.M.R. Spectra 105 1Q 1 Roberts and coworkers have s t u d i e d the 7 F and H n.m.r. s p e c t r a of 1 , 1 - d i f l u o r o - 2 , 2 - d i c h l o r o - 3 - p h e n y l - 3 - m e t h y l c y c l o b u t a n e , C F 2 C C 1 2 C ^ C 6 H 5 ^ ( C H 3 ^ H 2 » a n d f i n d t h a t t h e t w o f l u o r i n e atoms are i n e q u i v a l e n t and that there are four very d i s t i n c t v i c i n a l H-F c o u p l i n g c o n s t a n t s . These r e s u l t s t o g e t h e r : w i t h those of other 6k 106.107 w o r k e r s l e d R o b e r t s t o suggest t h a t when a l a r g e s u b s t i t u e n t i s a t t a c h e d t o one o f the c a r b o n atoms o f the c y c l o b u t a n e r i n g t h e n the r i n g i s l o c k e d i n a no n - p l a n a r c o n f o r m a t i o n . I f I t i s assumed t h a t a c y c l o b u t a n e r i n g i s no n - p l a n a r t h e n s u b s t i t u e n t s would occupy a t l e a s t p a r t i a l " a x i a l " or p a r t i a l " e q u a t o r i a l " pos-105 i t i o n s s i m i l a r t o thos e o f c y c l o h e x a n e . R o b e r t s and cowork e r s suggest t h a t the degree o f p u c k e r i n g may be c o n s i d e r a b l e s i n c e the c h e m i c a l s h i f t s o f the geminal f l u o r i n e atoms o f 1 , 1 - d i f l u o r -ocyc l o b u t a n e s d i f f e r by 7-15 p.p.m. wh i c h i s t o be compared w i t h a d i f f e r e n c e o f 15«5 p.p.m. f o r 1 , 1 - d i f l u o r o c y c l o h e x a n e when i t undergoes slow r i n g i n v e r s i o n a t -80°. The s i m p l e s t *H n.m.r. spectrum o b t a i n e d i n the p r e s e n t i n -v e s t i g a t i o n i s t h a t o f l , 2 - d i c h l o r o - 3 , 3 » 4 > 4 " t e t r a f l u o r o c y c l o b u t -y l ' t r i m e t h y l germane ( F i g u r e 2 ) . I f t h e c y c l o b u t a n e r i n g i s puck-e r e d t h i s compound c a n have one of f o u r s t r u c t u r e s , V I I , V I I I , I X or X. 65 V I I a n d I X a r e a l m o s t c e r t a i n . t o be f a v o u r e d s i n c e t h e b u l k y t r i -m e t h y l g e r m y l g r o u p w o u l d be i n a n " e q u a t o r i a l " p o s i t i o n . I t w i l l be a s s u m e d i n f u r t h e r d i s c u s s i o n s o f t h e * H n . m . r . s p e c t r a o f o t h e r c y c l o b u t a n e s p r e p a r e d i n t h i s i n v e s t i g a t i o n t h a t t h e t r i -m e t h y 1 - s i l y l , - g e r m y l a n d - s t a n n y l g r o u p s o c c u p y " e q u a t o r i a l " p o s -i t i o n s . T o d i s t i n g u i s h b e t w e e n i s o m e r s V I I a n d I X a q u a n t i t a t i v e s t u d y o f t h e c o u p l i n g c o n s t a n t s i s n e c e s s a r y . P h i l l i p s * ^ 0 was a b l e t o a s s i g n c o u p l i n g c o n s t a n t s f o r l - p h e n y l - 3 , 3 , 4 > 4 - t e t r a f l u o r o c y c l o -b u t a n e o n a f i r s t - o r d e r b a s i s s i n c e t h e r e i s no m e a s u r a b l e c o u p -l i n g b e t w e e n t h e v i c i n a l f l u o r i n e s . F i g u r e ' 2 g i v e s a n a s s i g n m e n t o f t h e c o u p l i n g c o n s t a n t s f o r 1 , 2 - d i c h I o r o - 3 , 3 , k > k - t e t r a f l u o r o -c y c l o b u t y l t r i m e t h y l g e r m a n e o n a f i r s t - o r d e r b a s i s . T h e f a c t t h a t f i r s t - o r d e r a s s i g n m e n t s c o r r e c t l y a c c o u n t f o r t h e s p a c i n g s a n d i n t e n s i t i e s i n t h e * H n . m . r . s p e c t r u m o f t h e g e r m a n e a p p e a r s t o i n d i c a t e t h a t s e c o n d o r d e r e f f e c t s a r e s m a l l . The a s s i g n e d v i c i n a l " a x i a 1 - a x i a 1" H - F c o u p l i n g o f 12 c p s i s j u s t i f i e d f r o m t h e a s s i g n m e n t o f 2 0 . 5 c p s f o r t h e same c o u p l i n g 105 i n 1 , 1 - d i f l u o r o - 2 - d i c h l o r o - 3 - p h e n y 1 - 3 - m e t h y l c y c l o b u t a n e a n d 108 e l e c t r o n e g a t i v i t y e f f e c t s . A b r a h a m a n d C a v a l l i h a v e s t u d i e d e x t e n s i v e l y t h e d e p e n d e n c e o f v i c i n a l H - F c o u p l i n g i n e t h a n e s o n t h e - e l e c t r o n e g a t i v i t i e s o f t h e r e m a i n i n g s u b s t i t u e n t s a n d h a v e f o u n d , t h a t a s t h e e l e c t r o n e g a t i v i t i e s o f t h e s u b s t i t u e n t s i n c r e a s e t h e v i c i n a l H - F c o u p l i n g d e c r e a s e s , e . g . C H 3 C H F 2 J H F ( v i c i n a l ) = 2 0 . 8 c p s C H . J C C I F 2 J p j p ( v i c i n a l ) = 15«0 c p s C H ^ C F ^ J ^ p ( v i c i n a l ) = 12.7 c p s C H X 1 C F ' j ' ( v i c i n a l ) = 8 . L 1 c p s t- j> Hr I n v i e w o f t h e s e r e s u l t s t h e a s s i g n e d v a l u e o f J H „ o f 12 c p s ( F i g -67 u r e 2) a p p e a r s r e a s o n a b l e . 109 H a l l a n d M a n s v i l l e f i n d t h a t f o r f l u o r i n a t e d s u g a r s t h e v i c i n a l " a x i a l - a x i a l " H - F c o u p l i n g i s t w o t o t h r e e t i m e s t h a t o f v i c i n a l " a x i a l - e q u a t o r i a l " H - F c o u p l i n g . T h u s J U _ i s a s s i g n e d a v a l u e o f k c p s . T h e a s s i g n e d v a l u e o f t h e same c o u p l i n g c o n -s t a n t f o r 1 , 1 - d i f l u o r o - 2 , 2 - d i c h l o r o - 3 ~ p h e n y 1 - 3 - m e t h y l c y c l o b u t a n e i s 9.k c p s 1 ^ , a n d i n v i e w o f A b r a h a m ' s a n d C a v a l l i ' s 1 ^ r e s u l t s t h e d e c r e a s e f r o m 9 . k t o k c p s f o r J o n g o i n g f r o m t h e 1 , 1 - d i -f l u o r o c y c l o b u t a n e t o t h e g e r m a n e d o e s n o t a p p e a r u n r e a s o n a b l e . T h e 8 c p s c o u p l i n g a s s i g n e d t o t h e • " a x i a l - a x i a l " H - F c o u p l i n g , J ' H F s e e m s t^e b e r e a s o n a b l e i n v i e w o f t h e v a l u e o f 2 .1 c p s f o r k " a x i a l - a x i a l " C H ^ - F c o u p l i n g i n 1 , 1 - d i f l u o r o - 2 , 2 - d i c h l o r o - 3 - p h e n -y 1 - 3 - n i e t h y l c y c l o b u t a n e T h e H - F c o u p l i n g c o n s t a n t s f o r v i c i n a l " e q u a t o r i a l H - e q u a t o r -i a l F " a n d ' E q u a t o r i a l H - a x i a l F " c o n f o r m a t i o n s i n 1 , 1 - d i f l u o r o -2 , 2 - d i c h l o r o - 3 - p h e n y l - 3 - m e t h y l e y c l o b u t a n e a r e 1.8 a n d 13.7 c p s r e s p e c t i v e l y * ^ . B e c a u s e o f t h e i n c r e a s e o f t h e e l e c t r o n e g a t i v -i t i e s o f t h e s u b s t i t u e n t s t h e s e c o u p l i n g 1 c o n s t a n t s c o u l d b e e x -p e c t e d - t o b e o f t h e o r d e r o f 1 a n d 8 c p s f o r t h e g e r m a n i u m d e r -i v a t i v e . I f t h e g e r m a n i u m d e r i v a t i v e i s a s s i g n e d s t r u c t u r e I X t h i s w o u l d m e a n t h a t J ^ p a n d J j ^ p m u s t be a s s i g n e d v a l u e s o f . 12 a n d k c p s w h i c h a p p e a r s t o b e v e r y u n r e a s o n a b l e . T h u s o n t h e b a s i s o f t h e c o u p l i n g c o n s t a n t s l , 2 - d i c h l o r o - 3 , 3 j k , k - t e t r a f l u o r o -c y c l o b u t y l . t r i m e t h y l g e r m a n e i s a s s i g n e d t h e t r a n s c o n f i g u r a t i o n . T h e m a j o r i s o m e r o f l - c h l o r o - 3 , 3 > 4 A - t e t r a f l u o r o c y c l o b u t y l -2 - t r i m e t h y l g e r m a n e i s a l s o a s s i g n e d t h e t r a n s c o n f i g u r a t i o n . 5 s i g n 1 -~~4x 68 The d o w n f i e l d p r o t o n a t -k.56 p.p.m. i s a s s i g n e d t o s i n c e t h i s p r o t o n i s e x p e c t e d t o be more_/cieshie ld«d than.FL^. The r e s o l u t i o n of the *H n.m.r. spectrum o f the c h l o r o c y c l o b u t y l g e r m a r t e i s not s u f f i c i e n t t o measure c o u p l i n g c o n s t a n t s . However, the w i d t h of the spectrum o f H^ a l l o w s f o r an approximate assignment of 8 cps f o r J i f i t i s assumed t h a t the r e m a i n i n g c o u p l i n g c o n s t a n t s are a p p r o x i m a t e l y eqiual t o the c o u p l i n g , c o n s t a n t s a s s i g n e d t o the 1 , 2 - d i c h l o r o c y c l o b u t y l g e r m a n e ( F i g u r e 2 ) . T h i s c o u p l i n g , J ~, 8 c p s , i s the o r d e r expected f o r v i e i n a l " a x i d l - a x i a l " p r o t o n coup-The *H n.m.r. s p e c t r a o f the m o n o c h l o r o c y c l o b u t y l g e r m a n e i s o -mers show t h a t t h e r e i s no l - c h l o r o - 3 , 3 , 4 > 4 " t e t r a f l u o r o c y c l o b u t y 1 -1-trimethylgermane formed s i n c e the d i f f e r e n c e i n c h e m i c a l s h i f t between, " a x i a l " a n d . " e q u a t o r i a 1 " geminal protons; i s expected t o 105 be of the or d e r o f 0.£ p.p.m. whereas the measured d i f f e r e n c e i n the r e l e v a n t s p e c t r a i s a p p r o x i m a t e l y 2 p.p.m. The, c o n f i g u r a t i o n of the group IV h y d r i d e - p e r f l u o r o c y c l o -butene adducts i s gi v e n . b e l o w (see a l s o F i g u r e s 3 and k ) . The a s s i g n e d c o u p l i n g c o n s t a n t s f o r a l l t h r e e 1:1 adducts. a r e com-1 p i l e d i n T a b l e V. The H n.m.r. spectrum of a l l t h r e e adducts show the pre s e n c e o f o n l y one isomer. The geminal c o u p l i n g con-s t a n t s , J u r , are r e a d i l y a s s i g n e d f r o m . r e s u l t s o b t a i n e d by o t h e r . 10Q w o r k e r s V H a l l and M a n s v i l l e 7 f i n d t h a t geminal H-F c o u p l i n g i n some f l u o r i n a t e d s u g ars (six-membered s a t u r a t e d r i n g s y s t e m s ) , F i g u r e 3 : H n . m . r . S p e c t r u m o f 1 - H - H e x a f l u o r o c y c l o b u t y l - 2 - t r i m e t h y l g e r m a n e 71 w i t h r e m a i n i n g s u b s t i t u e n t s o f c o m p a r a b l e e l e c t r o n e g a t i v i t y t o t h a t o f t h e - C F 2 - • a n d - C F M ^ H ^ ) - g r o u p s , v a r i e s f r o m 51.9 t o 53'4 c p s . C l a r k a n d c o w o r k e r s * * * a s s i g n a v a l u e o f 57 c p s f o r t h e g e m i n a l HF c o u p l i n g , i n 1 , 1 , 2 , 2 - t e t r a f l u o r o e t h y l t r i m e t h y l t i n , ( C H ^ ) ^ S n C F ^ C F ^ H . T h e s e r e s u l t s i n d i c a t e t h a t t h e J ^ p ^ a s s i g n m e n t s o f 52 ( s i l a n e ) , 55 ( g e r m a n e ) a n d 55 c p s ( t i n ) a r e c o r r e c t . T A B L E V H - F C O U P L I N G CONSTANTS OF T H E 1:1 F L U O R O C Y C L O B U T E N E - H Y D R I D E A D D U C T S ' CF—CH M X JHFo< J H F ^ A x - A x S i Ge S n Ge . F F c F d C l e 22 22 22.5 52 55 55 v l 3 1 3 - 7 12.5 12 ( C H 3 ) 3 M C X — C X ^ H b b b b C o m p o u n d V i c i n a l G e m i n a l V i c i n a l T h r o u g h 1+ b o n d s A x - E q A x - A x A x - E q ~6'. <v»7 ~1.5 5-5 7.0 1.7 5.0 7.5 2.5 k . O 8.0 $1 a 1 f- F r o m H n . m . r . s p e c t r a c p s c . F i g u r e 3 a F i g u r e k . e F i g u r e 5 When t h e * H n . m . r . s p e c t r u m o f l , 2 - d i c h l o r o - 3 , 3 j 4 A ~ t e t r a f l u o r o -c y c l o b u t y l t r i m e t h y l g e r m a n e i s c o m p a r e d w i t h t h a t o f t h e p e r f l u o r o -c y c l o b u t e n e - h y d r i d e a d d u c t s ( T a b l e V) i t i s r e a d i l y s e e n t h a t t h e c o u p l i n g o f 22-22.5 c p s , c a n . be a s s i g n e d t o J - . H a l l a n d M a n s -v i l i e 1 0 9 f i n d t h a t t h e v i c i n a l . " a x i a l - a x i a l " " H F c o u p l i n g i n f l u o r -i n a t e d s u g a r s v a r i e s f r o m ' 23«4 to.25.k- c p s . T h e v i c i n a l " a x i a l -e q u a t o r i a l " H - F c o u p l i n g i s c o n s i d e r a b l y l e s s (8.0 t o 11.7 c p s ) . T h u s t h e a d d u c t s a r e a s s i g n e d t h e t r a n s H F ^ c o n f i g u r a t i o n a n d t h e " a x i a l - a x i a l " H F ^ c o n f o r m a t i o n . T h e r e m a i n i n g c o u p l i n g c o n s t a n t s o f t h e p e r f l u o r o c y c l o b u t e n e a d d u c t s a r e a s s i g n e d i n a n a n a l o g o u s 7 2 m a n n e r t o t h e c o u p l i n g c o n s t a n t s t h a t w e r e a s s i g n e d t o 1 , 2 - d i -c h l o r o - 3 , 3 » i | r , i + - t e t r a f l u o r o c y c l o b u t y l t r i m e t h y l g e r m a n e ( F i g u r e 2) . (3) P r o p o s e d M e c h a n i s m s T h e *H n . m . r . s p e c t r a o f t h e 1:1 p e r f l u o r o c y c l o b u t e n e - h y d r i d e a d d u c t s i n d i c a t e t h a t t h e y h a v e a t r a n s " a x i a l - a x i a l " H-F c o n -f i g u r a t i o n s u c h a s w o u l d b e f o r m e d b y c i s a d d i t i o n o f t h e t r i -m e t h y 1 - s i l a n e , - g e r m a n e a n d t r i m e t h y l t i n h y d r i d e a c r o s s t h e d o u b l e b o n d . I t a p p e a r s o n t h i s b a s i s t h a t a f o u r - c e n t r e m e c h a n i s m i s m o s t r e a s o n a b l e w i t h a t r a n s i t i o n s t a t e a s f o l l o w s : 2: r ' z '« | | r> M = S i , G e , S n fcH3)3A— -H A f r e e r a d i c a l m e c h a n i s m c o u l d a l s o a c c o u n t f o r t h e c i s a d -d i t i o n , v i z . ( a ) ( C H 3 ) 3 M H +. G F = C F C F 2 G F 2 • ( C H ^ M - + CFHCFc72"cF2 ( b ) C F H C F C F 2 C F 2 + ( C H ^ M H * C F H C F ( M ( C H 3 ) 3 ) C F 2 C F 2 + H-I n e q u a t i o n ( b ) ( G H 3 ) 3 M H w o u l d a t t a c k t h e p s e u d o " e q u a t o r i a l " p o s i t i o n a n d t h e h y d r o g e n w o u l d b e i n a p s e u d o " a x i a l " p o s i t i o n t o g i v e a t r a n s " a x i a l - a x i a l " H-F c o n f i g u r a t i o n . H o w e v e r , t h e r a d -i c a l m e c h a n i s m d o e s n o t e x p l a i n t h e q u a n t i t a t i v e y i e l d o f t h e g e r -mane o r t i n d e r i v a t i v e s ( t h e l a t t e r s u b s e q u e n t l y s l o w l y d e c -o m p o s e s a f t e r f o r m i n g ) s i n c e i t s e e m s t h a t a d d i t i o n a l p r o d u c t s w o u l d be f o r m e d b y t h e f o l l o w i n g r e a c t i o n s : C F H - C F C F 2 O F 2 + ( C H ^ M H * C F H C F H C F 2 6 F 2 + ( C H ^ M -2 ( C H 3 ) 3 M - • ( C H 3 ) 3 M M ( C H 3 ) 3 ( C H 3 ) 3 M - + ( C H ^ M H -+ ( C H 3 ) ^ M e t c . T h e s t a b i l i t y o f t h e 1:1 p e r f l u o r o c y c l o b u t e r i e - s i l a n e a n d 73 - g e r m a n e a d d u c t s a t 250 a n d 230° r e s p e c t i v e l y a g r e e s w i t h t h e r e s u l t s o b t a i n e d b y H a l u s k a ^ who f o u n d t h a t h e a t i n g t o 350-600° w a s n e c e s s a r y t o e l i m i n a t e h y d r o g e n f l u o r i d e f r o m 1 - H - h e x a f l u o r o -c y c l o b u t y 1 - 2 - d i c h l o r o m e t h y l s i l a n e . C H 3 S i ( C l 2 ) C R F C F H C F 2 C F 2 — H F + C H ^ S i ( C 1 2 ) C = C F G F " ^ C F 2 T h e d e c o m p o s i t i o n o f t h e 1:1 p e r f l u o r o c y c l o b u t e n e - t i n . a d d u c t s t o t i n f l u o r i d e s i s t o be e x p e c t e d i n v i e w o f t h e r e s u l t s o f r e l a t e d 12 s t u d i e s . C l a r k a n d c o w o r k e r s o b t a i n e d d i m e t h y l t i n d i f l u o r i d e f r o m t h e r e a c t i o n s o f t r i f l u o r o e t h y l e n e a n d ' 1 , 2 - d i f l u o r o e t h y l e n e w i t h d i m e t h y l t i n d i h y d r i d e . ( c ) , ( C H 3 ) 2 S n H 2 + C F 2 = C F H ( d ) ( C H 3 ) 2 S n H 2 + CFH=CFH C F H = C F H + ( C H 3 ) 2 S n F 2 C H 2 = C H F + ( C H 3 ) 2 S n F 2 ( C H 3 ) 2 S r ( C F 2 C F H j 2 -( C H 3 ) 2 S r ( C F H C F H 2 ) 2 ~ T h e s e w o r k e r s o b t a i n e d some e v i d e n c e t h a t t h e r e a c t i o n s p r o c e e d , a s i n d i c a t e d , by a d d i t i o n f o l l o w e d b y e l i m i n a t i o n a l t h o u g h t h e a d -d i t i o n p r o d u c t s c o u l d n o t . b e i s o l a t e d a n d c o n c l u s i v e l y i d e n t i f i e d . T h e y f o u n d , h o w e v e r , t h a t t h e a d d i t i o n p r o d u c t s , ( C H 3 ) 2 S n ( H ) C F 2 C F p H a n d ( C H 3 ) 2 S n ( C F 2 C F 2 H ) 2 , f r o m . t h e r e a c t i o n o f t e t r a f l u o r o e t h y l e n e a n d d i m e t h y l t i n d i h y d r i d e a r e s t a b l e w i t h r e s p e c t t o t h e e l i m -112 i n a t i o n o f t i n f l u o r i d e s . T h e r m o c h e m i c a l d a t a o b t a i n e d by S w a r t s i n d i c a t e t h a t i t r e q u i r e s a p p r o x i m a t e l y 10 k c a l / m o l e m o r e e n e r g y t o b r e a k a C - F b o n d i n t h e - C F 2 ~ g r o u p t h a n t h e C - F b o n d i n t h e - C F H - g r o u p . T h u s t h e s t a b i l i t y o f c o m p o u n d s s u c h a s ( C H 3 ) 2 S n -( C F 2 C F 2 H ) 2 a n d ( C H 3 ) 2 S n (H) C F g C F g H a n d t h e i n s t a b i l i t y o f ( C H - ^ S n -( C F H C F H 2 ) 2 a n d ( C H 3 ) 2 S n ( H ) C F H C F H 2 w o u l d be e x p e c t e d . H o w e v e r t h e i n s t a b i l i t y o f ( C H ) 2 S n ( C F 2 C F H 2 ) 2 t o f o r m t i n f l u o r i d e a n d t h e 12 o l e f i n , C F H = C F H , i s u n e x p e c t e d . C l a r k a n d c o w o r k e r s do n o t corn-mi t t h e m s e I v e s a s t o t h e d i r e c t i o n o f a d d i t i o n ( t h e p o s t u l a t e d i n -t e r m e d i a t e ( C H 3 ) 2 S n ( C F 2 C F H 2 ) 2 i s *the a u t h o r ' s c h o i c e b a s e d o n d i p o l e m o m e n t s ) , b u t r e g a r d l e s s o f w h e t h e r t h e i n t e r m e d i a t e a d -d i t i o n p r o d u c t i s ( C H ^ ) 2 S n ( C F H C F 2 H ) 2 o r ( C H ^ ) 2 S n ( C F 2 C F H 2 ) 2 o r 7k whether an a d d i t i o n product i s a c t u a l l y formed the r e a c t i o n prod-uct CFH=CFH and not CF2=CH2 (equation c) appears to have no t h e r -modynamic basis.. The d e h y d r o c h l o r i n a t i o n of c h l o r o a l k y l s i l a n e s has been ex-t e n s i v e l y i n v e s t i g a t e d 1 * 3 . Bases such as q u i n o l i n e 1 1 1 ^ cat-a l y z e t h i s e l i m i n a t i o n . S u b s t i t u t i o n of a l k y l groups f o r c h l o r i n e on the s i lane leads to a lower y i e l d of the v i n y l d e r i v a t i v e , e.g. CH2=CHC1 + H S i C l ^ » C H 2 = C H S i C T 3 (60%) CH 2=CHCr+ H S i C l 2 ( C 2 H ^ ) • CH 2=CHSiCl ( C ^ ) ( 2 7 % ) The r e a c t i o n of p o l y f l u o r o o l e f i n s c o n t a i n i n g c h l o r i n e has a l s o been i n v e s t i g a t e d . The a d d i t i o n of t r i c h l o r o s i l a n e to t r i f l u o r o -g c h l o r o e t h y l e n e r e s u l t e d i n s a t u r a t e d as w e l l as v i n y l d e r i v a t i v e s , HSiCl-j + CF 2=CFC1 > CFgHCClFSiCl^ + CFC1HCF 2SiC 1^ + C F ^ C F S i C l ^ These same r e a c t a n t s under d i f f e r e n t c o n d i t i o n s are r e p o r t e d to 9 give no v i n y l d e r i v a t i v e a s . w e l l as other product v a r i a t i o n s . Cl^SiH + CFC1=CF 2 i ^ L . C H F C l C F 2 S i C l 3 + S i C l ^ + CH^FCFgSiCl^ 9 Although Haszeldine and Young proposed a c h a i n of r a d i c a l reac-t i o n s to account f o r C H g F C F ^ i C l ^ and S i C l ^ t h e i r presence can a l s o be explairi-ed by an e l i m i n a t i o n f o l l o w e d by an a d d i t i o n reac-t i o n . C H F C l C F 2 S i C l 3 » S i C l ^ + CHF=CF 2 C l ^ S i H + CHFCF 2 » Cl^SiCFgCFgH However, somewhat anomalous r e s u l t s are r e p o r t e d f o r 1 , 1 , 2 - t r i -f l u o r o - 2 - c h l o r o e t h y 1 - 1 - t r i c h l o r o s i l a n e when i t i s heated to 2 5 0 ° ^. F l u o r o t r i c h l o r o s i l a n e and c h l o r o - 1 , 2 - d i f l u o r o e t h y l e n e are the major p r o d u c t s . C H F C l C F 2 S i C l 3 • C l ^ S i F + CHF=CFC1 T h i s appears to be i n c o n s i s t e n t i n view of the thermodynamic stab-112 i l i t y of the -CF - group and the absence of S i F e1iminated prod-75 113 u c t s i n the r e s u l t s of other workers On the b a s i s of these p r e v i o u s i n v e s t i g a t i o n s the r e a c t i o n of t r i m e t h y l s i l a n e w i t h . 1 , 2 - d i c h l o r o t e t r a f l u o r o c y c l o b u t e n e i n the present i n v e s t i g a t i o n i s thought to be an a d d i t i o n f o l l o w e d by competing e l i m i n a t i o n r e a c t i o n s . (CH ) SiH + CCl^ C C l c V J c F - • ( C H - ^ S l f c c i - C H C l c T ^ C F -• ( G H 3) 3S iCC1CHC1CF 2CF 2 — • ( C H 3 ) 3 S i C l + CC1=CHCF 2CF 2 + HCl + ( C H 3 ) 3 S i C = C C l C F 2 C F 2 The d e h y d r o c h l o r i n a t i o n of ch1oroaIkylgermanes i n the p r e s -117 ence of base or aluminum t r i c h l o r i d e has been observed H G e Cl 3 + CHC1=CHC1 - - ^ C l C H 2 C H C l G e C l 3 ClCH^CHClGeCl- T^rrw* CH o=CClGeCl 0 _ _> V-^n-N d. } Competing e l i m i n a t i o n products s i m i l a r to some r e s u l t s obtained from the c h l o r o a l k y l s i l a n e s r e a c t ions d e s c r i b e d above has a l s o 118 been observed f o r c h l o r o a l k y l g e r m a n e s . C1CH 2CH 2GeC1^ c 2 ^ ° ° > GeC1 k + CH 2=CHGeC1 3 " I t i s a l s o to be noted that the f o r m a t i o n of germanium t e t r a c h l o r -ide i n t h i s r e a c t i o n i n v o l v e s 1,2 e l i m i n a t i o n . No examples of f l u o r o o l e f i n s r e a c t i n g w i t h germanes have been p u b l i s h e d at p r e s -ent . The produdt f o r m a t i o n of the 1 , 2 - d i c h l o r o t e t r a f l u o r o c y c l o -butene- t r i m e t h y lgermane r e a c t i o n i n d i c a t e s the f o l l o w i n g . r e a c -t i o n scheme: (CH 3) 3GeH -f C C l = C C l C F 2 t F - * (CH-j) 3GeC6ICC 1HCF 2CF 2 ( f ) (CH 3) 3GeCC 1CHC1CF 2CF 2 • ( CH-^GeCl + CC1=CHCF 2CF 2 (g) (CH 3) 3GeCC1CHC1CF 2CF 2 • H C l + (CH 3) 3Ge6=CC1CF 2CF 2 '(h)' (CH 3) 3GeH + CC1=CHCF 2CF 2 • (CH3) 3GeCHCHC 1CF 2CF 2 ( i ) (CH 3) 3GeCHCHClCF 2CF 2 — * HCl + (CH 3) 3GeC=CHCF 2CF 2 The complete absence o f the o r i g i n a l 1:1 adduct (equation (e)) 76 from the thermal r e a c t i o n at 230° and i t s presence i n the thermal r e a c t i o n at 190° appear to i n d i c a t e i t s formation f o l l o w e d by decomposition a c c o r d i n g to (f) and ( g ) . Equations (h) and ( i ) are merely r e p e t i t i o n s of (e) and (g) to account f o r the,product form-a t i o n . The"*H,• n.m.r. r e s u l t s (page 6k) i n d i c a t e t h a t 1 , 2-di-c h l o r o - 3 , 3 > 4 > 4 - t e t r a f l u o r o c y c l o b u t y l t r i m e t h y l g e r m a n e has a t r a n s c o n f i g u r a t i o n which would i n v o l v e a c i s a d d i t i o n of the germane to the double bond. A four c e n t r e mechanism 'accounts f o r t h i s c i s a d d i t i o n and i s favoured i n the present i n v e s t i g a t i o n . The apparent presence of both c i s- and t r a n s - i somers f o r 1-chloro-3 , 3 > 4 , k - t e t r a f l u o r o c y c l o b u t y 1 - 2 - t r i m e t h y l g e r m a n e can not be ex-p l a i n e d on the b a s i s of a f o u r - c e n t r e mechanism. However, i t i s p o s s i b l e that a secondary r e a c t i o n between trimethylgermane and 1 , 2 - d i c h l o r o - 3 , 3 > ' K > k - t e t r a f l u o r o c y c l o b u t y l t r i m e t h y l g e r m a n e to form the c i s - and t r a n s - c h l o r o c y c l o b u t y l g e r m a n e d e r i v a t i v e without the i n t e r m e d i a t e formation of l - H - 2 - c h l o r o t e t r a f l u o r o c y c l o b u t e n e may occur. ( C H ^ G e H + ( C H 3 ) 3 G e C C l C H C l C F 2 C F 2 — > ( C H ^ G e C l + (CH^)^GeCHCHClCF 2CF 2 By analogy with the r e a c t i o n s d e s c r i b e d above i t appears reasonable to assume that a d d i t i o n f o l l o w e d by e l i m i n a t i o n a l s o accounts f o r the formation of t i n c h l o r i d e s from the 1 , 2 - d i c h l o r o -cyclobutene and -pentene r e a c t i o n s w i t h t i n h y d r i d e . There are.no known examples of d e h y d r o c h l d r i n a t i o n of c h l o r o a I k y l t i n comp-ounds but the p o s s i b l e e l i m i n a t i o n of t i n bromides from bromo-12 f l u o r o a l k y l t i n compounds has been reported ( C H 3 ^ 2 S n H 2 + CF^CFBr > (CH^.SnBr + ( C H ^ S n B r ^ + CFH=CF Although the a d d i t i o n products c o u l d not. be • i s o l a t e d ' there.was evidence suggesting t h e i r presence. 77 CHAPTER I I I I FLUOROACETYLENES INTRODUCTION The f l t i o r o a c e t y l e n e s , 1, 1, 1 - t r i f l u o r o p r o p y n e and h e x a f l u o r o -bu.t -2-yne were f i r s t p r e p a r e d about f i f t e e n y e a r s ago; the butyne 119 by d e c h l o r i n a t i o n o f 2 , 3 - d i c h l o r o h e x a f l u o r o b u t - 2 - e n e w i t h z i n c CF-,CC1=CC1CF. + Zn _ 1 T ^„ * CF QCECCF Q + Z n C l -j J CgH^OH J J <-and the propyne by the d e h y d r o h a l o g e n a t i o n of 1 , 1 , 1 - t r i f l u o r o - 3 -120 h a l o p r o p e n e . The butyne i s now c o m m e r c i a l l y a v a i l a b l e and the propyne i s more c o n v e n i e n t l y p r e p a r e d from the c o m m e r c i a l l y a v a i l -121 a b l e 1 , 1 , 1 - t r i f l u o r o t r i c h l o r o p r o p e n e as f o l l o w s CF 3CC1=CC1 2 + Zn » CF^CECZnCl or ( C F 3 C E C ) 2 Z n ^ — • C F 3 C E C H 122 H a s z e l d i n e s t u d i e d the a d d i t i o h of hydrogen h a l i d e s t o h e x a f l u o r o b u t - 2 - y n e and 1 , 1 , 1 - t r i f l u o r o p r o p y n e . A d d i t i o n t o 1,1,1-t r i f l u o r o p r o p y n e was found t o b e - a n t i Markovnikov. CF 3CECH.+ HX * CF 3CH=CXH I n v e s t i g a t i o n of the r e a c t i o n s of Group VI compounds w i t h these f l u o r o a c e t y l e n e s has been m a i n l y r e s t r i c t e d t o a l c o h o l s . Has-122 z e l d i n e added methane and e t h a n o l i n the presence of the r e s -p e c t i v e a l k o x i d e s t o h e x a f l u o r o b u t - 2 - y n e and 1 , 1 , 1 - t r i f l u o r o p r o p -yne. - . CF^CECCF^ + ROH ———» CF^C(OR)=CHCF 3 CF_C=CH + ROH * CF~CH=CHOR Chaney* 2- 3 o b t a i n e d both the mono- and d i a d d u c t s from.the a d d i t i o n of e t h a n o l and g l y o x a l to h e x a f l u o r o b u t - 2 - y n e . There are two ex-amples of the r e a c t i o n of s u l p h u r or s u l p h u r compounds t o the butyne. Krespan and c o w o r k e r s 1 ^ r e a c t e d hot s u l p h u r vapour and h e x a f l u o r o b u t - 2 - y n e and o b t a i n e d as one o f the p r o d u c t s a. d i s u l -p h ide group a c r o s s the t r i p l e - b o n d . 78 C F 3 C = C C F 3 + S * CF 3C=C(CF 3)-<Ts T h e o t h e r r e p o r t e d e x a m p l e i s t h e x - r a y c a t a l y z e d a d d i t i o n o f h y -' 125 d r o g e n s u l p h i d e t o h e x a f l u o r o b u t - 2 - y n e t o g i v e t h e m o n o - a d d u c t B y c o m p a r i s o n , s t u d i e s o f t h e r e a c t i o n s o f h e x a f l u o r o b u t - 2 -y n e w i t h G r o u p V c o m p o u n d s h a v e b e e n r e l a t i v e l y n u m e r o u s . H a s -122 z e l d i n e r e a c t e d s e c o n d a r y a m i n e s w i t h 1 , 1 , 1 - t r i f l u o r o p r o p y n e i a n d h e x a f l u o r o b u t - 2 - y h e a n d o b t a i n e d t h e m o n o a d d u c t s . C F 0 C = C C F _ + ( C 0 H _ , ) _ N H * C F _ C H = C ( CF_ ) N ( C 0 H _ , ) _ 3 3 2 5 2 3 3 2 5 2 O F ^ C E C H + ( C 2 H ^ ) 2 N H > C F 3 C H = C H N ( C ^ ) 2 12k .. o K r e s p a n r e a c t e d t h e b u t y n e w i t h r e d p h o s p h o r u s a t 200 i n t h e p r e s e n c e o f i o d i n e a n d o b t a i n e d a c y c l i c o l e f i n i c c o m p o u n d . C F 3 C = C C F 3 + P 3 T h e m o n o a d d u c t , 2 , 3 _ b i s ( d i p h e n y l p h o s p h i n o ) h e x a f l u o r o b u t - 2 - ; e n e was o b t a i n e d w h e n t e t r a p h e n y l d i p h o s p h i n e a n d h e x a f l u o r o b u t - 2 - y n e w e r e h e a t e d t o 1.30° 1 2 ^ . T h e b u t y n e a d d s t o d i p h e n y l p h o s p h i n e a t . 20° t o g i v e t h e m o n o a d d u c t 1 2 ° . ( C ^ H ^ ) 2 P H + C F 3 C s C G F 3 *• ( ) 2 P ( C F 3 ) G=CHCF. 3 C u l l e n a n d H o t a ^ " 1 f o u n d t h a t a r e a c t i o n b e t w e e n t e t r a m e t h y l d i a r -s i n e a n d 1 h e x a f l u o r o b u t - 2 - y n e o c c u r s r a p i d l y a n d q u a n t i t a t i v e l y a t r o o m t e m p e r a t u r e . ( C H 3 ) p A s - A s ( C H 3 ) 2 +; G F 3 C = C C F 3 * (CH-j) 2 A s C ( C F 3 ) = C ( G F 3 ) A s ( G H 3 ) 2 T h e b u t y n e d o e s n o t r e a c t w i t h t e t r a k i s ( t r i f l u o r o m e t h y l ) d i a r s i n e e v e n w h e n h e a t e d t o 100°. A n u m b e r o f s e c o n d a r y a r s i n e s h a v e b e e n r e a c t e d w i t h h e x a -126 f l u o r o b u t - 2 - y n e by C u l l e n - a n d c o w o r k e r s . D i m e t h y l a r s i n e a n d t h e b u t y n e r e a c t i m m e d i a t e l y o n m i x i n g t o g i v e 2 - d i m e t h y l a r s i n o -•1, 1 , l , k , k , k - h e x a f l u o r o b u t - 2 - e n e , p h e n y I m e t h y l a r s i n e a d d s s l o w l y t o 7 9 the butyne at 2 0 ° , and b i s ( t r i f l u o r o m e t h y 1 ) a r s i n e r e q u i r e s h e a t i n g to g i v e the a r s i n o b u t e n e . ( C F ^ g A s H + CF 3CaCCF 3 > (CF^ ) ^As (CF 3) C=C ( C F 3 ) H D i m e t h y l a r s i n e r e a c t s r e a d i l y w i t h 1 , 1 , 1 - t r i f l u o r o p r o p y n e t o g i v e 126 an i s o m e r i c m i x t u r e of butenes ( C H 3 ) 2 A s H + H C E C C F 3 * (CH 3 ) 2 A s C ( C F 3 ) = C H 2 + (CH 3) 2AsCH=CHCF 3 Upon u l t r a v i o l e t i r r a d i a t i o n or h e a t i n g h e x a f l u o r o b u t - 2 - y n e w i l l add t o c h l o r o d i m e t h y l a r s i n e but l i t t l e or no r e a c t i o n o c c u r s w i t h 127 v a r i o u s o t h e r c h l o r o a r s i n e s '. ( C H 3 ) 2 A s C l +:CF 3C=CCF 3 >• (CH^)2AsC(CF3)=CClCF3 ( C 6 H ^ ) 2 A s C l + CF 3C=CCF 3 > no r e a c t i o n The r e a c t i o n betwe\en h e x a f l u o r o b u t - 2 - y n e and t r a n s i t i o n metal compounds, i n p a r t i c u l a r t r a n s i t i o n metal c a r b o n y l s , has been i n v e s t i g a t e d by two groups of w o r k e r s . W i l k i n s o n and coworkers 128,129 r e a c t e d the butyne w i t h a number of t r a n s i t i o n m e tal c a r b o n y l s and t r a n s i t i o n metal c a r b o n y l e y e l o p e n t a d i e n y 1 compounds and ob-t a i n e d a v a r i e t y of p r o d u c t s , e.g. QQ I 1*-CGF. C O 2CF 3C=CCF 3 + Fe(CO)^ O / S I CCF, --Mn(CO) 3 > <^ H-Mn*-]!| •> ; Fe(C0) 3 Stone and c o w o r k e r s * 3 ^ ' ^  found t h a t h e x a f l u o r o b u t - 2 - y n e w i l l add to manganese pentacarbony 1 h y d r i d e and rhenium pentacarbony 1 hy-d r i d e t o g i v e the r e s p e c t i v e butenes. (CO)^MH-+ CF 3C=CCF 3 ». (CO)^MC(CF 3)=CHCF 3 M = Mn, Re In the f o l l o w i n g e x p e r i m e n t a l and d i s c u s s i o n s e c t i o n s the 80 r e a c t i o n o f h e x a f l u o r o b u t - 2 - y n e a n d 1 , 1 , 1 - t r i f l u o r o p r o p y n e ' w i t h some G r o u p IV a n d G r o u p V o r g a n o m e t a 1 1 i c c o m p o u n d s i s d e s c r i b e d . 81 E X P E R I M E N T A L The g e n e r a l e x p e r i m e n t a l t e c h n i q u e a n d a p p a r a t u s h a s b e e n p r e v i o u s l y d e s c r i b e d i n C h a p t e r I , p a g e 6 • A . G r o u p I V H y d r i d e s ( 1 ) S t a r t i n g M a t e r i a l s H e x a f l u o r o b u t - 2 - y n e was p u r c h a s e d f r o m P e n i n s u l a r C h e m r e s e a r c h , a n d i t s p u r i t y was c h e c k e d by i t s i n f r a r e d s p e c t r u m . T h e 1 , 1 , 1 -t r i f l u o r o p r o p y n e was a g i f t f r o m c o w o r k e r M . W o o l l e n d s . ( a ) T r i e t h y l g e r m a n e - - B r o m o t r i e t h y l g e r m a n e was p r e p a r e d by h e a t i n g t e t r a e t h y l g e r m a n e ( 0 . 1 m o l e e x c e s s ) a n d b r o m i n e a t 100° f o r o n e d a y . A f t e r r e m o v a l o f t h e v o l a t i l e m a t e r i a l t h e r e s u l t -i n g b r o m o t r i e t h y l g e r m a n e a n d t e t r a e t h y 1 g e r m a n e m i x t u r e was u s e d f o r t h e p r e p a r a t i o n o f t r i e t h y 1 g e r m a n e . T h i s m i x t u r e was d i s -s o l v e d i n 1M h y d r o b r o m i c a c i d a n d r e d u c e d by s o d i u m b o r o h y d r i d e ^ . The w o r k - u p n e c e s s i t a t e d r e p e a t e d e x t r a c t i o n s w i t h d i e t h y l e t h e r a n d t h e n d r y i n g o v e r c a l c i u m c h l o r i d e f o r t w o d a y s . T r i e t h y l g e r -mane was p u r i f i e d by d i s t i l l a t i o n , b . p . 120-125° ( l i t . v a l u e 1 2 k -125°) ( 1 2 % y i e l d ) a n d i t s p u r i t y was c h e c k e d by i t s i n f r a r e d s p e c -t r u m . -( b ) T i n H y d r i d e s - - T h e p r e p a r a t i o n o f t r i m e t h y l t i n h y d r i d e h a s b e e n p r e v i o u s l y d e s c r i b e d i n C h a p t e r I , p a g e l k . T r i e t h y l t i n h y -d r i d e was s i m i l a r l y p r e p a r e d i n d i e t h y l e t h e r a n d p u r i f i e d by t r a p - t o - t r a p d i s t i l l a t i o n a n d i t s p u r i t y c h e c k e d by i t s i n f r a r e d . s p e c t r u m . D i b u t y l t i n d i h y d r i d e was a l s o s i m i l a r l y p r e p a r e d f r o m t h e c o r r e s p o n d i n g d i c h i o r i d e i n d i e t h y l e t h e r . T h e s o l v e n t was d i s t i l l e d o f f a n d t h e r e m a i n i n g l i q u i d w a s t a k e n a s d i b u t y l t i n d i h y d r i d e . T r i b u t y l t i n h y d r i d e was p r e p a r e d by t h e a d d i t i o n o f ammonium c h l o r i d e t o a s o l u t i o n : o f t r i b u t y l t i n s o d i u m i n l i q u i d 131 a m m o n i a . T r i b u t y l t i n c h l o r i d e was a d d e d t o s o d i u m - 1 i q u i d am-82 m o n i a s o l u t i o n f o r t h e p r e p a r a t i o n o f t r i b u t y l t i n s o d i u m . T r i -b u t y l t i n h y d r i d e was p u r i f i e d by d i s t i l l a t i o n , b . p . 7 5 ° (2 mm) ( l i t . v a l u e 6 5 - 6 7 ( 0 . 6 mm)) a n d i t s p u r i t y c h e c k e d by i t s i n -f r a r e d s p e c t r u m . (2) R e a c t i o n s w i t h F l u o r o a c e t y l e n e s ( a ) R e a c t i o n o f T r i m e t h y l s i l a n e a n d E x c e s s H e x a f l u o r o b u t - 2 - y n e - - T r i m e t h y l s i l a n e ( 2 . 1 g) a n d h e x a f l u o r o b u t - 2 - y n e (11 . 1 g) w e r e i r r a d i a t e d w i t h u l t r a v i o l e t l i g h t for 11 d a y s . U n r e a c t e d b u t y n e ( 7 - 4 5 g) w h i c h w e n t t h r o u g h a - 9 6 ° t r a p was r e c o v e r e d . T h e m a i n p r o d u c t , 1, 1, 1 , k , k , k - h e x a f l u o r o b u t e n y l t r i m e t h y 1 s i l a n e ( 5 . 1 g , 73%), b . p . 9 7 - 9 8 ° (754 mm), w h i c h w e n t t h r o u g h a - 2 3 ° t r a p a n d c o n d e n s e d i n a - 9 6 ° t r a p ( F o u n d : C , 3 5 . 3 ; H , k . 2 ; F , 1+7.9 %. C a l c . f o r G 7 H 1 0 F 6 S i : C ' 3 ^ , 6 ; H ' k ' 2 ; F , I+8.3 %) . I n f r a r e d s p e c t r u m ( l i q u i d f i l m ) : 2995 w, 2912 w, 11+21 w , 1351+ s , 1300 m, 1257 v s , l l l + l v s , ' 91+8 m, 883 m, 81+9 s , 771 m, 693 m, 659 w, 6 k l m c m - 1 . N . m . r . s p e c -t r a : t h e * H n . m . r . s p e c t r u m s h o w e d a b r o a d m e t h y l a b s o r p t i o n a t 0 . 1 0 p . p . m . a n d a n o l e f i n i c p r o t o n a b s o r p t i o n a t - 6 . 3 8 p . p . m . a s a q u a r t e t o f q u a r t e t s ( J = 8 . 8 a n d 2 . 5 c p s ) o f r e l a t i v e i n t e n s i t y 1 : 9 . 0 ( C a l c . 1 : 9 - 0 ) . A - 2 3 ° f r a c t i o n ( 2 . 0 g) h a d 7 c o m p o n e n t s a c c o r d i n g t o v . p . c . a n a l y s i s ( 5 1 U c o n P o l a r a t 1 1 0 ° ) . T h e m a i n c o m p o n e n t , a p p r o x -i m a t e l y 65% by w e i g h t , was c o l l e c t e d a n d i d e n t i f i e d a s a h e x a -f l u o r o b u t e n e b i s ( t r i m e t h y 1 s i l a n e ) , b . p . 7 9 ° (38 mm) ( F o u n d : C , 3 8 . 7 ; H , 6 . 5 ; F , 3 6 . 9 %; m o l . w t . ( c a m p h o r ) , 307 - C a l c . f o r G 1 0 H 2 0 F 6 S i 2 : C ' 3 8 ' 7 ; H , 6 . 5 ; F , 3 6 . 8 %', m o l . w t . , ' 3 1 0 ) . I n f r a -r e d s p e c t r u m ( l i q u i d f i l m ) : 2988 m, 2920 m, 11+23 m, 1367 s , 1335' m, 1285 s , ; 1259 s , 1239 m, 1181 w ( s h ) , 1165 w ( s h ) , l l k 6 s , 1071 s , _ . T h e S n - H i n f r a r e d a b s o r p t i o n s a n d t h e b o i l i n g p o i n t s o f some t i n h y d r i d e s a r e t a b u l a t e d i n a r e c e n t r e v i e w 1 3 2 > 8 3 1028 m, 886 m, 8kk s, 777 m, 762 w, 7 k l m, 693 m cm N.m.r. spec-t r a : the *H n.m.r. spectrum showed a broad methyl a b s o r p t i o n at 0.1.0 p.p.m. and a methine m u l t i p l e t at - 1 . 6 6 p.p.m. of r e l a t i v e i n t e n s i t y 1 : 8 . 8 ( C a l c . 1 : 9 . 0 ) . The ^ F n.m.r. spectrum showed doublets at - 2 1 . 8 p.p,.m. (J = 13 cps) and - 2 3 . 6 p.p.m. ( J = 12 cps) of equal i n t e n s i t y . (b) R e a c t i o n of Excess T r i m e t h y l s i l a n e with Hexafluorobut - 2-yne --The s i lane (3«5 g) and the butyne ( 2 . 1 g) were i r r a d i a t e d f o r 11 days. Unreacted t r i m e t h y l s i l a n e ( 2 . 1 g) which went through a - 7 8 ° trap was recovered. The monoadduct, 1 , 1 , 1 , k , L , k - h e x a f l u o r o b u t -eny l t r imethy Is i lane ( l . k g ) t and the diadduct ( 2 . 0 g) were prod-uced and i d e n t i f i e d by t h e i r i n f r a r e d s p e c t r a . A second experiment of excess t r i m e t h y l s i l a n e ( 7 . 7 6 g) and hexafluorobut - 2-yne (k .06 g) produced the monoadduct ( 3 - 5 2 g) and the diadduct ( 2 . 0 2 g) a f t e r 7 days i r r a d i a t i o n w i t h u l t r a v i o l e t 1i ght. (c) R e a c t i o n of T r i m e t h y l s i l a n e and the Monoadduct--Trimeth-y l s i l a n e (3«55 g) and 1 , 1 , 1 , k , k , k - h e x a f l u o r o b u t e n y 1 t r i m e t h y 1 s i l a n e V I ( 1 . 8 5 g) were i r r a d i a t e d f o r 11 days. U n r e a c t e d • t r i m e t h y l s i l a n e . ( 3 - 5 g) and monoadduct ( 1 . 6 5 g) were recovered. Some diadduct ( 0 . 2 5 g) was produced and i d e n t i f i e d by i t s i n f r a r e d spectrum. (d) Thermal R e a c t i o n of T r i m e t h y l s i l a n e . and Excess H e x a f l u o r o -but - 2-yne -- . ' T r i m e t h y l s i l a n e ( 0 . 8 2 g) and the butyne ( 6 . 2 6 g) were heated at 235° f ° r 7 hours. Unreacted butyne (k .06 g) which went through a - 7 8 ° trap was recovered. The monoadduct ( 1 . 7 3 g) was produced as I d e n t i f i e d by i t s i n f r a r e d and H^ n.m.r. s p e c t r a . N.m.r. spec-, • 1 V t.ra: the H n.m.r.* spectrum showed methyl a b s o r p t i o n s at 0 . 16 and 0 . 1 0 p.p.m. ( r e l a t i v e i n t e n s i t y 1 :15 .6) and o l e f i n i c proton,mul-t i p l e t s at -5.'72p.p.m. (J = 8 . 3 and 4 0 . 6 cps) and. - 6 . 3 2 p.p.m. 8L ( J = 8 . 6 a n d 2 . 5 c p s ) . A - 2 3 ° f r a c t i o n ( 1 . 2 9 g) was f o u n d t o c o n t a i n n i n e c o m p o n -e n t s by v . p . c . a n a l y s i s (10* s i l i c o n e a t 1 8 0 ° ) . None o f t h e s e was i d e n t i f i e d . ( e ) T h e r m a l R e a c t i o n o f E x c e s s T r i m e t h y l s i l a n e a n d H e x a f l u o r o -b u t - 2 - y n e - - _ \ T r i m e t h y l s i l a n e ( 5 . 7 0 g) a n d t h e b u t y n e ( 2 . 7 7 g) w e r e h e a t e d a t 2 3 5 ° f o r 7 h o u r s . A n u n i d e n t i f i e d f r a c t i o n ( 0 . 1 g) w h i c h c o n -. o t a i n e d C - F b a n d s a n d w h i c h w e n t t h r o u g h a -96 t r a p was p r o d u c e d . A - 9 6 ° f r a c t i o n (4-16 g) w h i c h w e n t t h r o u g h a - 7 8 ° t r a p was f o u n d t o c o n t a i n a m i x t u r e o f t e t r a m e t h y l s i l a n e a n d t r i m e t h y l s i l a n e ( i d -e n t i f i e d by i n f r a r e d a n d * H n . m . r . s p e c t r a ) a l o n g w i t h a s m a l l am-o u n t o f i m p u r i t y . T h e m i x t u r e was a n a l y z e d q u a n t i t a t i v e l y by * H n . m . r . t o c o n t a i n t r i m e t h y l s i l a n e ( 2 . 2 g) a n d t e t r a m e t h y l s i l a n e . ( 1 . 8 g ) . T h e b u t e n y 1 t r i m e t h y l s i l a n e ( c i s : t r a n s , 1:10 by n . m . r . a n a l y s i s ) ( 2 . 9 4 g) w a s r e c o v e r e d i n a - 7 8 ° t r a p a n d i d e n t i f i e d by i t s i n f r a r e d a n d * H n . m . r . s p e c t r a . T h e d i a d d u c t , t h e b u t e n e b i s -t r i m e t h y l s i l a n e ( 1 . 2 7 g)> was a l s o p r o d u c e d . T h e d i a d d u c t w a s h e a t e d a t 2 3 5 ° f o r 7 h o u r s a n d was r e c o v e r e d q u a n t i t a t i v e l y a f t e r t h i s p e r i o d o f h e a t i n g . ( f ) T h e r m a l R e a c t i o n o f T r i m e t h y l s i l a n e a n d T r a n s - 1 , 1, 1, 4 , 4» ^J- - H e x a f l u o r o b u t e n y l t r i m e t h y l s i l a n e - - T r i m e t h y l s i l a n e ( 3 - 3 4 g) a n < 3 t h e b u t e n y l s i l a n e ( 3 - 0 2 g) w e r e h e a t e d a t 2 3 5 ° f o r 7 h o u r s . U n r e a c t e d t r i m e t h y l s i l a n e ( 3 - 3 4 g) was r e -c o v e r e d . T h e r e c o v e r e d m o n o a d d u c t ( 2 . 9 5 g) was i n a c i s - t r a n s r a t i o o f 1 :6.1 f r o m * H n . m . r . a n a l y s i s . T h e c i s - t r a n s r a t i o o f t h e m o n o a d d u c t was u n c h a n g e d a f t e r 3 d a y s o f u l t r a v i o l e t i r r a d i a t i o n w i t h o r w i t h o u t t h e p r e s e n c e o f e i t h e r t r i m e t h y l s i l a n e o r h e x a f l u o r o b u t - 2 - y n e . A f t e r 4 d a y s h e a t -i n g a t 235° a c i s - t r a n s r a t i o , o f 1:6 o f t h e m o n o a d d u c t was u n c h a n g e d . 85 S i m i l a r l y a f t e r 20 h o u r s a t 235° t h e t r a n s m o n o a d d u c t f r o m t h e u l t r a v i o l e t r e a c t i o n was l e s s t h a n 15% c o n v e r t e d t o t h e c i s - i s o m e r (g) R e a c t i o n o f T r i e t h y l g e r m a n e a n d H e x a f l u o r o b u t - 2 - y n e - - T r i -e t h y l g e r m a n e ( 1 . 2 g) a n d t h e b u t y n e ( k . l g) w e r e i r r a d i a t e d f o r o n e w e e k . U n r e a c t e d h e x a f l u o r o b u t y n e (2.8 g) was t h e o n l y v o l -a t i l e f r a c t i o n . T h e i n v o l a t i l e f r a c t i o n ( 2 . k g) was d i s t i l l e d t o g i v e 1 , 1 , 1 , k , k , k - h e x a f l u o r o b u t e n y l t r i e t h y l g e r m a n e , b . p . 82° (26 mm) ( F o u n d : C , 3 7 . 8 ; H , k . 7 %. C a l c . f o r C ^ H ^ G e F ^ : C , 3 7 - 2 ; H , 5 - 0 •%)'. I n f r a r e d s p e c t r u m ( l i q u i d f i l m ) : 2930 m, l k 6 6 w l k 3 5 w, 1383 w, 1369 w , 1 3 k l s , 1293 m, 1257 v s , l l k 2 v s , 1020 w ( 1010 m, 973 w, 880 w, 850 w, 720 w, 706 m c m - 1 . N . m . r . s p e c t r a l t h e * H n . m . r . s p e c t r u m s h o w e d a p e a k a t - 0 . 8 7 p . p . m . ( - C g H ^ ) a n d m u l t i p l e t s a t - 5 - 8 2 p . p . m . ( q u a r t e t , J =-8 a n d ^ 1 c p s ) a n d - 6 . 5 9 p . p . m . ( J = 8 . 0 a n d 2 . 5 c p s ) . T h e r e l a t i v e i n t e n s i t y o f t h e e t h y l p e a k t o t h e d o w n f i e l d p e a k s i s 1:15-9 ( C a l c . 1 : 15 .0) a n d t h e r e l -a t i v e i n t e n s i t y o f t h e t w o d o w n f i e l d m u l t i p l e t s i s 1:11. A f t e r h e a t i n g t h i s i s o m e r i c m i x t u r e o f t h e b u t e n y l g e r m a n e f o r k5 h o u r s a t 220° t h e r e w a s l i t t l e o r n o c h a n g e i n t h e i s o m e r d i s t r i b u t i o n a l t h o u g h c o n s i d e r a b l e d e c o m p o s i t i o n h a d o c c u r r e d . ( h ) R e a c t i o n o f T r i m e t h y l t i n H y d r i d e a n d H e x a f l u o r o b u t - 2 - y n e - - T r i m e t h y l t i n h y d r i d e ( 2 . 9 g) a n d t h e b u t y n e ( 6 . 9 g) g a v e a n e x -o t h e r m i c r e a c t i o n i m m e d i a t e l y o n m i x i n g . U n r e a c t e d b u t y n e ( k . l g.) w h i c h w e n t t h r o u g h a -70 t r a p was r e c o v e r e d . T h e r e a c t i o n p r o d -u c t ( 5 - 9 g) w h i c h c o n d e n s e d i n a - 7 8 t r a p w a s i d e n t i f i e d a s t h e k n o w n c o m p o u n d , 1 , 1 , 1 , k , k , k - h e x a f l u o r o b u t e n y l t r i m e t h y l t i n , b . p . 12k° (751 mm), b y means o f i t s i n f r a r e d a n d * H n . m . r . s p e c t r a ( s e e a l s o ( 2 ) ( a ) p a g e ) . N . m . r . s p e c t r a : t h e * H n . m . r . s p e c -t r u m s h o w e d a p e a k a t - 0 . 1 5 p . p . m . ( - C H ^ ) a n d a m u l t i p l e t a t - 6 . 5 7 p . p . m . ( J = 7-5 a n d 2 . 3 c p s ) o f r e l a t i v e i n t e n s i t y 1 : 8 . 8 ( C a l c . 86 1 : 9 - 0 ) , and a l s o showed that only one isomer was prese n t . ( i ) R e a c t i o n of T r i e t h y l t i n Hydride and Hexafluorobut - 2-yne--T r i e t h y l t i n hydride ( 5 . 7 g) and the butyne ( 8 . 2 5 g) gave an im-mediate exothermic r e a c t i o n on mixing. Unreacted butyne ( 3 - 3 §.) . was recovered. The remaining f r a c t i o n ( 1 0 . 3 g) was i d e n t i f i e d as 1 , 1 , 1 , k , k , L - h e x a f l u o r o b u t e n y 1 t r i e t h y I t i n , b.p. 86° (24 mm) (Found: C, 3 2 . 5 ; H, 4 - 0 ; Sn, 3 2 . 0 ; F, 3 0 . 9 %.. C a l c . f o r C 1 0 H l 6 F 6 S n : C, 3 2 . 5 ; H, 4 - 3 ; Sn, 3 2 . 2 ; F, 3 0 . 9 %). I n f r a r e d spectrum ( l i q u i d f i l m ) : 2930 m, 2900 w (sh), 2860 w (sh), 2820 w (sh), 1469 m, 1454 m, 1382 m, • 1368 w ( s h ) , 1352 w, 1326 s, 1290 m, 1253 vs, 1190 w ( s h ) , 1137 vs, 1005 m, 961 m, 848 m, 717 w, 675 m. era" 1. N.m.r. s p e c t r a : the V n.m.r. spectrum showed peaks at - 1 . 0 1 and - 1 . 0 5 p.p.m. (-C H_0 and a m u l t i p l e t at - 6 . 6 1 p.p.m.. (J = 7-5 and 2 p 2 . 4 c p s ) . The r e l a t i v e i n t e n s i t y of the e t h y l a b s o r p t i o n to the m u l t i p l e t i s 1: II4. (Calc . 1 :-l5) • The c i s-trans isomer r a t i o i s 1:50 from v.p.c. a n a l y s i s ( 5 ' Ucon P o l a r at 1 5 0 ° ) . (j) R e a c t i o n of T r i b u t y l t i n Hydride and Hexafluorobut - 2-yne--T r i b u t y l t i n h y dride (7*1 g) and the butyne ( 8 . 8 5 g) gave a v i g -orous exothermic r e a c t i o n immediately on mixing. Unreacted but-yne ( 5 - 0 g) was recovered. The i n v o l a t i l e f r a c t i o n . (1 1 . 0 g) was i d e n t i f i e d as 1 , 1 , 1 , 4 , 4 > 4 _ h e x a f l u o r o b u t e n y I t r i m e t h y I t i n , b.p. 7 2 ° (10 J mm) (Found: C, 4 2 . 0 ; H, 6 . 3 ; Sn, 2 6 . 4 ; F, 2 5 . 7 mol. wt. , 2 3 8 . C a l c . f o r .C l 6H 2gF 6Sn: C, 4 2 . 4 ; H, 6 . 2 ; Sn, 2 6 . 2 ; F, 2 5 . 2 % ; mol. wt., 2 5 3 ) . I n f r a r e d spectrum ( l i q u i d f i l m ) : 2982 s, 2917 s, 2870 m, 1470 m, 1426 w, 1382 m, 1356 w, 1330 s, 1295 m, 1255 vs, 1144 vs, 1075 m, 1048 w, 1024 w, 1001 w, 962 w, 881 m, 850 m, 717 674 m> °36 m c m N.m.r. sp e c t r a : the *H n.m.r. spectrum showed 19 a m u l t i p l e t at - 6 . 6 0 p.p.m. (J = 7-5 and 2 . 3 cps) and the . F n.m. 87 spectrum showed a peak at -10.9 p.p.m. and a broad doublet at -11.3 p.p.m. (J ~ 7 cps) . The c i s-trans isomer r a t i o i s 1:12 from v.p.c. a n a l y s i s (5 1 Ucon Po l a r at 105°). (k) R e a c t i o n of D i b u t y l t i n D i h y d r i d e and Hexafluorobut-2-yne--•The d i h y d r i d e (3-1 9) and hexafluorobutyne (16.8 g) react e d im-mediately on mixing. Unreacted butyne (13-7 g) was recovered as the only v o l a t i l e f r a c t i o n . The i n v o l a t i l e f r a c t i o n (6.2 g) gave a white s o l i d on standing i n d i c a t i n g the presence of impur-i t y i n the b i s ( 1 , 1 , 1 , k , k , k - h e x a f l u o r o b u t e n y l ) d i b u t y 1 t i n , b.p. 63° (10 3 mm). An a n a l y t i c a l sample was obtained by v.p.c. (5' Ucon P o l a r at 160°) (Found: C, 3k .2 ; H, 3.3; Sn, 20.3; F, k0.5 % . C a l c . f o r c 1 ^ H 2 o F i l | S n : C » 3k.k; H, 3.6; Sn, 21.2; F, k 0 . 8 % ) . I n f r a r e d spectrum (1 i q u i d f 1 l m ) : 2981 m, 2915 m, 2875 m, lk68 m, 11+25 w, 1382 m, 1358 w, 1329 s, 1295 m, 1255 vs, 1139 vs, I O 7 8 m, 10k8 w, 1025 w, 998 w, 960 w, 920 w, 883 m, 718 w, 670 m cm - 1. N.m.r. s p e c t r a : t h e * H n.m.r. spectrum shows a downfield o l e -f i n i c p r oton at -6.6k p.p.m. ( J = 7 and 1.5 cps) . The r e l -a t i v e i n t e n s i t y of t h i s m u l t i p l e t to the u p f i e l d b u t y l peaks i s 1:9.k ( C a l c . 1:9-0). (1) R e a c t i o n , o f T r i m e t h y l t i n Hydride and Excess 1 , 1 , 1-Tri-f luoropropyne -- ;  T r i m e t h y l t i n h y d r i d e (5-75 g) and the propyne (k-65 g) were l e f t . at 20° f o r one day. Unreacted propyne (2.35 g) which went through a -96° t r a p was recovered. Unreacted t r i m e t h y l t i n hydride (1.7 g) which went through a -k6° t r a p condensed i n a -96° t r a p . The monoadduct^ 1 , 1 , 1 - t r i f l u o r o p r o p e n y l t r i m e t h y l t i n . (3.9 g), b.p. 129° (756 mm), condensed i n a -k6° trap (Found: C, 27.6; H, k .2 % . C a l c . f o r C.H F.Sn: C, 27.8; 'H, k-3 %)• I n f r a r e d spectrum ( l i q u i d 6 1 1 3 f i l m ) : 3005 w, 2932 w, 1619 w, 1356 w, 1313 m, 1278 vs, 1215 s, 88 1203 m ( s h ) , I I 8 3 w, l l ^ l w ( s h ) , 1117 v s , 985 m, 968 v w , 838 w , 771 s , 719 w, 689 w cm N . m . r . s p e c t r a : t h e *H n . m . r . s p e c -t r u m ( F i g u r e 5.) s h o w e d m e t h y l a b s o r p t i o n a t 0 . 0 0 a n d - 0 . 0 5 p . p . m . a n d t w o d i s c e r n i b l e d o w n f i e l d o l e f i n . p r o t o n p a t t e r n s ; t h e t r a n s i s o m e r s h o w e d a b s o r p t i o n s a t - 5 - 8 2 (Hg) a n d - 6 . 8 l p . p . m . (H_.). w i t h J i 4 u = 19 .2 c p s , J „ ( g e m i n a l ) = 5*3 c p s , a n d J ( v i c i n a l ) = n n "(3^^ ^ H ^ C F ^ 1.9 c p s ; t h e j s o i s o m e r s h o w e d a b s o r p t i o n s a t . [4.8 a n d - 6 . I 8 p . p . m . w i t h J •=. 1.5 a n d J u r P = 2 . 3 a n d ^ 1 c p s . T h e r e l a t i v e i n t e n s i t y HH ". H C F 3 F 7 o f t h e m e t h y l a b s o r p t i o n s t o t h e d o w n f i e l d o l e f i n i c a b s o r p t i o n s i s k . 6 : 1 ' ( C a l c . k . 5 ' 1) • T h e i s o m e r d i s t r i b u t i o n b y H n . m . r . s p e c t r u m o f t h e m o n o a d d u c t d i d n o t c h a n g e a f t e r d i s t i l l a t i o n . A l -t h o u g h t h r e e d i f f e r e n t c o l u m n s w e r e u s e d , 10-' U c o n P o l a r , 10' s i l -i c o n e , a n d 10' A p i e z o n J , t h e i s o m e r s c o u l d n o t be s e p a r a t e d by v . p . c . A n i n v o l a t i l e f r a c t i o n (2.1+ g) , b . p . 108° (29 mm), a n a l y z e d a s t h e d i a d d U c t , 1 , 1 , 1 - t r i f l u o r o - 3 , 3 - h i s ( t r i m e t h y I t i n ) p r o p a n e ( F o u n d : C , 25>.k; H , k . 6 •%. C a l c . f o r c 9 H 2 1 F 3 S n 2 : c > 25.5»- H , 5 .0%). I n f r a r e d s p e c t r u m ( l i q u i d f i l m ) : 3000 m, 2930 m, II4.I4.7 m, 1385 w, 1362 m, 1311 m, 1279 w , 1259 s , 1213 s , 1193 w ( s h ) , 1133 s , 1110 m, 1078 s , 1050 w , 1022 m, 893 m, 828 m, 812 w, 761 s , 71k. m, 677 w c m " 1 . " 1 N . m . r . s p e c t r a : t h e H n . m . r . s p e c t r u m s h o w e d a p e a k a t - .0 .20 p . p . m . ( - C H ) a n d a m u l t i p l e t a t - 2 . 5 8 p . p . m . ( - C H - ) ( J = 8 . 0 a n d 1 0 . 5 c p s ) . T h e r e l a t i v e i n t e n s i t y o f t h e m e t h y l e n e a b s o r p t i o n t o t h e m e t h y l a b s o r p t i o n was 1:10 ( C a l c . 1 : 9 ) . (m) R e a c t i o n o f E x c e s s T r i m e t h y l t i n H y d r i d e a n d 1 , 1 , 1 - T r i -f l u o r o p r o p y n e - - \ T r i m e t h y l t i n h y d r i d e ( 2 . 0 g) a n d t r i f l u o r o p r o p y n e ( 1 . 0 5 9) w e r e l e f t a t 20° f o r k d a y s . U n r e a c t e d a c e t y l e n e ( 0 . 5 g) a n d u n r e a c -t e d t r i m e t h y l t i n h y d r i d e ( O . k g) w e r e r e c o v e r e d . The m o n o a d d u c t ( 1 . 1 g) a n d t h e d i a d d u c t ( 1 . 0 g) w e r e p r o d u c e d a n d i d e n t i f i e d by 89 t h e i r i n f r a r e d s p e c t r a . ( n ) R e a c t i o n o f T r i m e t h y l t i n H y d r i d e a n d 1 , 1 , 1 - T r i f l u o r o -p r o p e n y 1 t r i m e t h y I t i n • ' ' ' '• , o T h e h y d r i d e ( 2 . 2 g) a n d t h e m o n o a d d u c t ( 1 . 6 g) w e r e l e f t a t 20 for 2 d a y s . T h e m o n o a d d u c t ( 1 . 6 g ) , Q% c i s i s o m e r by * H n . m . r . a n a l y s i s , a n d t r i m e t h y l t i n h y d r i d e ( 2 . 0 g) w e r e r e c o v e r e d . A n i n v o l a t i l e f r a c t i o n ( 0 . 2 g) s h o w e d o n l y w e a k C - F a b s o r p t i o n s i n t h e . i n f r a r e d s p e c t r u m . ( o ) R e a c t i o n p f D i m e t h y l a m i n e a n d 1 , 1 , 1 - T r i f l u o r o p r o p y n e - - . D i m e t h y l a m i n e ( 1 . 2 g) a n d t h e p r o p y n e ( 6 . 0 g) g a v e a v i g o r o u s e x o t h e r m i c r e a c t i o n i m m e d i a t e l y o n m i x i n g . U n r e a c t e d p r o p y n e ( k . l g) w h i c h w e n t t h r o u g h a i - 9 6 ° t r a p was r e c o v e r e d . A - 9 6 ° f r a c t i o n ( 2 . 1 g) w h i c h c o u l d n o t be f u r t h e r s e p a r a t e d was i d e n t -i f i e d a s t h e 1: 1 a d d v i c t , b . p . 1 1 8 ° (759 mm) ( F o u n d : C , I4 .3.O; H , 5 . 7 ; F , k l . O ; N , 10 .3 %. C a l c . f o r C ^ H g F ^ N : C , k 3 . 2 ; H , 5 - 8 ; F , .[(.1.0; 'N, 10.1 %) . I n f r a r e d s p e c t r u m ( 1 i q u i d f i l m ) : 2915 m, 2820 w, 1736 w, 1660 v s , l k 8 8 w, li|.k7 m, 1362 s , 1307 s , 1258 s , 1229 s , 115k vw ( s h ) , 1102 w, 1076 v s , 96O s , 888 s , 8k5 m, 739 m, 678 s cm N . m . r . ' b p e . c t r a : t h e * H n . m . l r . s p e c t r u m s h o w e d a p e a k a t ' - 2 . 2 9 p . p . m . ' ( - C H ^ ) a n d m u l t i p l e t s o f e q u a l i n t e n s i t y a t . -3 .66 a n d - 6 . 1 7 p . p . m . ( J . n , = 13.0 c p s a n d • J u ^ , „ = 6 . 5 a n d 1.5 c p s ) . T h e r l n n U r ^ r e l a t i v e i n t e n s i t y o f t h e o l e f i n i c m u l t i p l e t s t o t h e m e t h y l a b -s o r p t i o n i s 1:3 ( C a l c . 1 :3)• A n i n v o l a t i l e f r a c t i o n ( 0 . 9 §) w h i c h r e m a i n e d i n t h e C a r i u s t u b e , h a d t h e same g e n e r a l i n f r a r e d s p e c t r u m a s t h e d e c o m p o s i t i o n p r o d u c t f r o m t h e d i s t i l l a t i o n o f t h e 1:1 a d d u c t - - t h e r e c o v e r y o f t h e 1:1 a d d u c t was a p p r o x i m a t e l y 25% u p o n d i s t i l l a t i o n . B . M e t a l - M e t a l B o n d s ( 1) S t a r t i n g M a t e r i a l s ' ' ( a ) H e x a e t h y l d i g e r m a n e - - B r o m o t r i e t h y l g e r m a n e a n d . s o d i u m w e r e 90 h e a t e d a t 290° i n a C a r i u s t u b e f o r o n e d a y 1 ^ . D i s t i l l a t i o n o f t h e i n v o l a t i l e l i q u i d g a v e a 35% y i e l d o f h e x a e t h y l d i g e r m a n e , b . p . 80° ( 0 . 5 mm) ( l i t . v a l u e 6 9 - 7 2 ° ( 0 . 1 m m ) ) 1 3 k . ( b ) H e x a m e t h y l d i t i n - - T e t r a m e t h y I t i n was p r e p a r e d b y a d d i n g s t a n n i c c h l o r i d e t o a n e x c e s s o f . m e t h y l m a g n e s i u m i o d i d e i n d i - n -b u t y l e t h e r , s t a n n i c b r o m i d e was p r e p a r e d by d r o p p i n g a , c a r b o n -. x ; " • • 135 t e t r a c h l o r i d e - b r o m i n e V s o l u t i o n o n t o . f i n e l y d i v i d e d t i n , a n d t r i m e t h y l t i n b r o m i d e was p r e p a r e d by t h e ' ' a d d i t i o n o f t e t r a m e t h y 1 -, , , , 136 t i n (3 m o l e s ) t o s t a n n i c b r o m i d e (1 m o l e ) . T h e t r i m e t h y l t i n b r o m i d e was a d d e d t o a s o d i u m - l i q u i d a m m o n i a s o l u t i o n a n d t h e r e s u l t i n g h e x a m e t h y l d i t i n was p u r i f i e d : b y d i s t i l l a t i o n , b . p . 1 2 2 ° 1 ^ 7 (132 mm) ( l i t . v a l u e 182° (756 mm) a n d i t ' s p u r i t y c h e c k e d by i t s i n f r a r e d s p e c t r u m . H e x a b u t y l d i t i j i was p u r c h a s e d f r o m C o l u m b i a O r g a n i c C h e m i c a l s a n d ' i t s p u r i t y c h e c k e d ..by m i c r o a n a l y s i s ( F o u n d 1 : C , 4 9 - 5 ' H , 9 . 1 ; S n , k O . O %. C a l c . f o r C ^ H ^ S n - , : C , k 9 - 7 ; H , 9 - 3 ; S n , k 0 . 9 %)> The t e t r a k i s ( t r i f l u o r o m e t h y 1) d i a r s i n e was a g i f t f r o m ' W ; . R . C u 11 e n . (2) R e a c t i o n s w i t h H e x a f l u o r o b u t - 2 - y n e ( a ) H e x a m e t h y l d i t i n - - T h e d i t i n ( 5 . 2 g) a n d t h e b u t y n e ( 8 . 0 g) w e r e i m m i s c i b l e a t 2 0 ° . H e a t i n g a t 100° f o r 2 d a y s r e s u l t e d i n ; c o n s i d e r a b l e r e a c t i o n w i t h u n r e a c t e d b u t y n e ( 6 . 5 g) b e i n g r e c o v -e r e d . ' • T h e ' r e m a i h i rig ' 1 i q u i d s h o w e d ' o n l y " w e a k C - F : a b s o r p t i o n s i n ' t h e i n f r a r e d s p e c t r u m . T h e r e m a i n i n g s o l i d i n t h e C a r i u s t u b e was e x t r a c t e d w i t h e t h e r ' a n d r e c r y s t a 111 z e d f r o m a c e t i c a c i d . T h e s o l i d was i d e n t i f i e d a s t r i m e t h y l t i n f l u o r i d e ( 0 . 5 g) by i t s i n -f r a r e d s p e c t r u m a n d . X - r a y p o w d e r 1 p h o t o g r a p h . When t h e d i t i n c o m p o u n d ( 6 . 2 g) a n d t h e a c e t y l e r i e ( 6 ; 1 g) w e r e i r r a d i a t e d w i t h u l t r a v i o l e t l i g h t f o r 2 d a y s one l i q u i d p h a s e was 91 p r o d u c e d . U n r e a c t e d h e x a f l u o r o b u t - 2 - y n e (3*0 g) w a s r e c o v e r e d . T h e i n v o l a t i l e c o l o u r l e s s l i q u i d r e s i d u e ( 9 . 3 g) d i s t i l l e d a t -3 ' s o 10 mm w i t h some d e c o m p o s i t i o n . A f r a c t i o n b o i l i n g a t 2 9 - 3 0 ( 1 0 ~ 3 mm) w a s i d e n t i f i e d a s h e x a m e t h y l d i t i n . A f r a c t i o n b o i l i n g a t 53° (10~ 3 mm) was i d e n t i f i e d a s t h e e x p e c t e d 1:1 a d d u c t , h e x a -f l u o r o - 2 , 3 ~ b i s ( t r i m e t h y l s t a n n y l ) b u t - 2 - e n e ( F o u n d : C , 2 k . 7', H , 3 . 8 ; F , 2 3 . 0 ; S n , k 8 . k %. C a l c . f o r Q 1 0 H i 8 i r 6 S n 2 : c>.2k-5'> H , 3 . 7 * F , . 2 3 . 3 ; S n , k 8 . 5 %). I n f r a r e d s p e c t r u m ( 1 i q u i d f i l m ) : 2960 m, 2885 m, 1685 m, 1308 w , 1261 m, 1235 v s , 1185 m, 1130 v s , 1015 m, 8k7 w, 767 s , 692 w, 6 k 2 m cm 1 . N . m . r . s p e c t r a : t h e * H n . m . r . ' s p e c t r u m o f a 25% s o l u t i o n i n a c e t o n e s h o w e d a b r o a d a b s o r p t i o n a t - 0 . 3 k p . p . m . ( J ~ 0 . 8 c p s ) . T h e ^ F n . m . r . s p e c t r u m s h o w e d o n l y o n e b r o a d p e a k a t - 2 1 . 8 p . p . m . Q u a l i t a t i v e b a s e h y d r o l y s i s o f t h e 1:1 a d d u c t (70° f o r k d a y s ) g a v e o n l y a t r a c e . o f a m i x t u r e o f c i s - a n d t r a n s - 1 , 1 , 1 , k ; U » k - h e x a -f l u o r o b u t e n e o f k n o w n i n f r a r e d s p e c t r u m . A s a m p l e o f t h e 1:1 a d -d u c t was h e a t e d a t 150° f o r 18 h o u r s . T h e d e c o m p o s i t i o n p r o d -u c t s w e r e w o r k e d up by t r a p - t o - t r a p d i s t i l l a t i o n . A - 7 8 ° f r a c -t i o n ( 0 . 3 5 g) w h i c h w e n t t h r o u g h a - k 6 ° t r a p c o n t a i n e d m o s t l y t e t -r a m e t h y I t i n a s i d e n t i f i e d b y i t s m o l e c u l a r w e i g h t o f 181 ( C a l c : .179) a n d i t s v . p . c . r e t e n t i o n t i m e ( A p i e z o n J a t 100°: ( C H ^ ^ S n , 17 m i n . 50 s e c . ; s a m p l e , 17 m i n . 55 s e c . ) . . V . p . c . a n a l y s i s o f a - k 6 ° f r a c t i o n ( 1 . 2 5 g) ( A p i e z o n j a t 120°) s h o w e d 5 c o m p o n e n t s . The f i r s t c o m p o n e n t was a h u n i d e n t i f i e d f l u o r o c a r b o n , a n d t h e t h i r d c o m p o n e n t , t h e m a i n d e c o m p o s i t i o n p r o d u c t ( 1 . 0 g) , was i d e n t i f i e d a s 1 , 1 , 1 , k > k » k " b e x a f l u o r o b u t e n y 1 t r i m e t h y 1 t i n ( F o u n d : C , 2 5 . 8 ; H , 3 . 0 ; - S n , 3 6 . O ; F , 3 5 - 1 %- C a l c . f o r C ^ H j ^ S n : C , 2 5 - 7 ; H , 3 . 1 ; S n , 3 6 . 3 ; F , 3 k . 9 %). I n f r a r e d s p e c t r u m ( l i q u i d f i l m ) : 2990 w , 2900 w , 1731 v w , l k l 7 w , 1392 v w , 1351 v w , 1328 s , 92 1291 m, 1255 vs, 1227 vw ( s h ) , 1210 vw (sh), 1200 vw (sh), 111+0 vs, -1 919 vw, 879 m, 81+9 m, 782 s, 728 w, 63L+ s cm . (b) Hexabutyldi t i n - - T h e d i t i n (11.5< g) and the butyne ( l £ . 0 g) were i r r a d i a t e d w i t h u l t r a v i o l e t l i g h t f o r 5 days. The v o l a t i l e f r a c t i o n (13.1+ g) contained, a number of f luorocarbons and was not f u r t h e r separated. The i n v o l a t i l e f r a c t i o n (12.1+ g) was - 3 d i s t i l l e d at 10 mm and gave a small amount of m a t e r i a l which came over at 6 1 - 6 3 ° and was i d e n t i f i e d as b i s ( 1,1, 1,!+,!+,l+-hexa-f luorobuteny 1) di-n-buty l t i n (Found: 1 C, 31+.0; H, 3.1+; F, 1+1.1+ %. C a l c . f o r C i 6 H 2 0 F 1 2 S n : C, 3I+.I+; H, 3 . 6 ; F, 1+0.8 %) . A l a r g e por-t i o n of the remaining i n v o l a t i l e s d i s t i l l e d at 7 0 - 1 0 0 ° (10 3 mm). The i n f r a r e d s p e c t r a of v a r i o u s c u t s showed a steady i n c r e a s e i n C'-H i n t e n s i t y and a decrease i n C-F1 i n t e n s i t y with d e c r e a s i n g v o l -a t i l i t y . The i n f r a r e d s p e c t r a were somewhat s i m i l a r t o the t i n h y d r i d e - h e x a f l u o r o b u t - 2 - y n e adducts. In a second experiment a f t e r i r r a d i a t i o n : f o r 28 hours d i s t --3 i l l a t i o n of the i n v o l a t i l e s at 10 mm r e s u l t e d i n the formation of t r i b u t y l t i n f l u o r i d e i n the s t i l l pot. The f l u o r i d e was; i d e n t -i f i e d by comparison of i'ts melting p o i n t with that of an a u t h e n t i c sample prepared from t r i b u t y l t i n c h l o r i d e and an aqueous s o l u t i o n of potassium f l u o r i d e . A f r a c t i o n which b o i l e d at 6 3 - 6 5 ° ( 10~ 3 mm.) was analyzed by v.p.c. (Ucon P o l a r at 11+0°) and found to c o n t a i n 9 components. The main component, the l a s t peak (50%" by weight), had a downfield q u a r t e t (J^Q cps) at ~5«88 p.p.m. i n i t s H n.m.r. spectrum. The i n f r a r e d spectrum of t h i s component was almost i d -e n t i c a l w i t h that of the r e a c t i o n product obtained from d i b u t y l -t i n d i h y d r i d e and hexafluorobut - 2-yne with a s l i g h t d i f f e r e n c e i n the CF r e g i o n and the appearance of two weak bands at 5-77 and 6.10 /Z<. The *H n.m.r. spectrum of the f i r s t 1+'components a l s o showed the prese ce of downfield protons a  q u a r t e t s ( J ~ 8 c p s ) . 93 ( c ) T e t r a k i s ( t r i f l u o r o m e t h y 1 ) d i a r s i n e - - T h e d i a r s i n e (1.1+ g) and hexafluorobut - 2-yhe ( 1 . 7 g) were i r r a d i a t e d f o r 1+ days and the 1:1 adduct, 2 , 3 - b i s ( b i s t r i f l u o r o m e t h y l a r s i n o ) h e x a f l u o r o b u t - 2 - e n e ( 0 . 6 g) was obtained (Found: C, .16.14.; F, 5 8 . 0 ; As, 25-7 %. C a l c . f o r . - C g A S g F j . g : C, 1 6 . 3 ; F, 5 8 . 2 ; As, 2 5 . 5 % ) . I n f r a r e d spectrum l i q u i d f i l m ) : " 1329 w, 1312+ w, 1253 vs, 1191 s, 1173 vs, 1151+ vs, 1132 s, 1120 vs, 1070 vs, 870 w, 808 w, 731 s, 711 w, 657 m cm" 1. On measuring the vapour pressure of the compound as a func-t i o n of temperature the f o l l o w i n g data were obtained f o r the arsinobutene: T°K p cm log p j x 1 0 3 ° K _ 1 297 0 . 3 0 - 0 . 5 2 3 . 3 7 3 H 0 . 7 5 8 - 0 . 1 2 3 . 2 1 325 1.529 +0.18 3.O8 339 2 . 7 8 9 +0.1+1+ 2 . 9 5 353 5 . 2 8 0 +0-.72 2 . 8 3 360 6 . 9 2 2 +0.81+ 2 . 7 8 A l i n e a r p l o t of log-p a g a i n s t y was obtained f o r t h i s narrow range. T h i s was used to give b.p. = 1 5 6 ° t 2° Lv = 10.3 t 0 . 5 kcal/mole Trouton's c o n s t . - 21+ - 1.5 e.u. Some decomposition was t a k i n g p l a c e on the mercury s u r f a c e at higher temperatures, thus only a narrow range of pressures.were recorded. Q u a l i t a t i v e base h y d r o l y s i s of the adduct at 100° gave only t r a n s - 1 , 1, 1,1+, 1+,l+-hexaf luorobut - 2-ene . (d) He xa ethy l d i germane --The digermane (2.1+ g) and h e x a f l u o r o -bUt - 2-yne (7 -6 g) were i r r a d i a t e d f o r 2 days. Unreacted butyne ( 7 . 6 g) was recovered. The remaining l i q u i d showed no C-F ab-s o r p t i o n s i n the i n f r a r e d . 91+ D I S C U S S I O N A . G r o u p I V H y d r i d e s ( 1) R e s u l t s T h e r e a c t i o n o f h e x a f l u o r o b u t - 2 - y n e w i t h t i n h y d r i d e s t o g i v e t h e h e x a f l u o r o b u t e n y l t i n c o m p o u n d s c a n be r e p r e s e n t e d by t h e g e n e r a l e q u a t i o n -s'nH + C F , C 3 C C F , — . - s ' n C C F ^ C H C F , I 3 3 , 3 3 T h e a d d i t i o n o c c u r s s p o n t a n e o u s l y a n d q u a n t i t a t i v e l y b e l o w r o o m t e m p e r a t u r e . T h u s h e x a f l u o r o b u t - 2 - y n e a d d s t o t r i m e t h y l t i n h y -d r i d e t o g i v e 1,1,1,k,k,k-hexafluorobuteny1trimethyIt i n , b . p . 12k° ' (751 mm). T h e p r o d u c t i s b e s t i d e n t i f i e d by i t s H n . m . r . s p e c -t r u m o f t w o s e t s o f p e a k s , t h e m e t h y l a b s o r p t i o n , a s i n g l e t - a t - 0 . 1 5 p . p . m . , a n d a n o l e f i n i c p r o t o n > a t - 6 . 5 7 p . p . m . ( r e l a t i v e i n t e n s i t y 1 : 8 . 8 ) . I t s * H n . m . r . s p e c t r u m a l s o s h o w s t h a t o n l y t h e t r a n s - i s o -mer i s p r e s e n t . T h e q u a r t e t o f q u a r t e t s a t - 6 . 5 7 p . p . m . , w i t h c o u p l i n g c o n s t a n t s 2 . 3 a n d 7-5 c p s a r i s e s b e c a u s e o f t h e t r a n s c o n f i g u r a t i o n ; 7-5 c p s i s t h e g e m i n a l C F ^ - H c o u p l i n g a n d 2 . 3 c p s i s t h e v i c i n a l c i s C F ^ - H c o u p l i n g . T h e s e a s s i g n m e n t s f o l l o w f r o m 16 t h e r e s u l t s o f p r e v i o u s i n v e s t i g a t i o n s . W i 1 f o r d a n d S t o n e f o r ( C O ) £ R e C ( C F 3 ) = C H C F 3 a s s i g n c o u p l i n g o f 9 . 1 c p s f o r g e m i n a l C F - - H 126 a n d 2 . 5 c p s f o r v i c i n a l c i s C F ^ - H . C u l l e n f o u n d t h a t f o r d i -m e t h y l a r s i no - 1, 1, 1, k , k , k - h e x a f l u o r o b u t e n e t h e g e m i n a 1 C F ^-H c o u p -l i n g f o r b o t h c i s - a n d t r a n s - i s o m e r s i s 8 . 3 c p s a n d t h a t t h e v i c -i n a l C F ^ - H c o u p l i n g f o r t h e t r a n s - a n d c i s - i s o m e r s i s 2 a n d ^ 1 c p s r e s p e c t i v e l y . I n a l l c a s e s o f b u t y n e a d d i t i o n t o G r o u p I V , h y d r i d e s t o g i v e t h e h e x a f l u o r o b u t e n y 1 d e r i v a t i v e s t h e t r a n s - i s o m e r p r e -d o m i n a t e s . T a b l e V I l i s t s t h e p r o d u c t s o b t a i n e d i n t h i s i n v e s t -i g a t i o n a n d g i v e s t h e p e r t i n e n t * H n . m . r . d a t a , t h e i s o m e r d i s t -r i b u t i o n a n d t h e b o i l i n g p o i n t s o f t h e s e h e x a f l u o r o b u t e n y 1 c o m p o u n d s . 95 T h e i s o m e r d i s t r i b u t i o n w a s a n a l y z e d e i t h e r b y v . p . c . o r by * H n . m . r . s p e c t r o s c o p y . I n t h e l a t t e r c a s e t h e t r a n s - i s o m e r i s d i s t -i n g u i s h e d f r o m t h e c i s - i s o m e r by t h e r e l a t i v e l y l a r g e v i c i n a l C F ^ - H c o u p 1 i n g . T A B L E V I DATA C O N C E R N I N G H E X A F L U O R O B U T E N Y L . D E R I V A T I V E S C F 3 C F 3 ^ c 7 \ J, H * C F ^ o H c=c / X ^ C F ^ X ( e p s ) J l J 2 S" ( c p s ) J l J 3 T r a n s b . p . ( C H 3 ) 3 S i ( C 2 H ^ ) 3 G e - 5 - 7 2 - 5 . 8 2 8 ^ 0 . 6 8 . 0 4 l - 6 . 3 9 - 6 . 5 9 8 . 8 8 . 0 2 . 5 2 . 5 100%^ 92%h 9 8 ° ( 7 5 k mm) 82° ( 2 6 mm) ( C 2 H 5 ) 3 S n ( n - C k H 9 ) 3 S n — ; ; - 6 . 6 1 - 6 . 6 0 7-5 7 . 5 2 . 5 2 . 3 9 8 % c 92%c 86° ( 2k mm) 7 2 ° ( 1 0 ~ 3 m m ) ( n - C k H 9 ) 2 S n d - - - 6 . 6 k .7 ,•4 .5 - 6 3 ° ( 1 0 " 3 m m ) ( C H 3 ) 3 S n ( C H _ ) „ A s 1 2 6 -5.1+8 8 . 3 ^ i - 6 . 5 7 - 6 . 5 0 7 . 5 8 . 3 2 . 3 2..0 ' 100% b ' Q6%h 1 2 k ° ( 7 5 l mm) C h e m i c a l s h i f t o f o l e f i n p r o t o n . 1'H n . m . r . d e t e r m i n a t i o n c V . p . c . d e t e r m i n a t i o n d ( n - C ^ H 9 ) 2 S n ( C ( C F 3 ) = C H C F 3 ) 2 Some c h a r a c t e r i s t i c a b s o r p t i o n s f o r t h e h e x a f l u o r o b u t e n y 1 d e r i v a t i v e s w h i c h a r e a t t r i b u t e d t o C - F s t r e t c h i n g modes a n d a n o l e f i n i c C - H d e f o r m a t i o n mode a r e g i v e n i n T a b l e V I I . T h e s i m -1 *5 ft i l a r i t y o f tlTe s p e c t r a i s r e a d i l y a p p a r e n t . B e l l a m y g i v e s a r a n g e o f 790-81+0 cm 1 f o r t h e s t r o n g CH o u t - o f - p l a n e d e f o r m a t i o n b a n d i n t h e i n f r a r e d s p e c t r u m . H o w e v e r i n t h e s p e c t r a o f t h e h e x a f l u o r o b u t e n y 1 d e r i v a t i v e s t h e r e a r e o n l y v e r y w e a k a b s o r p t i o n s i n t h i s r e g i o n (790-81+0 cm * ) ; c o n s e q u e n t l y , t h e m e d i u m a b s o r p t i o n 96 a t 81+9-850 cm 1 i s a s s i g n e d t o t h e C H o u t - o f - p l a n e d e f o r m a t i o n v i b r a t i o n . S t r o n g a b s o r p t i o n s i n t h e 1000-11+00 cm r e g i o n a r e c h a r a c t e r i s t i c o f f l u o r o c a r b o n d e r i v a t i v e s a n d c a n be a s s i g n e d t o 13 C - F s t r e t c h i n g v i b r a t i o n s . A n i n t e r e s t i n g o b s e r v a t i o n i s t h a t t h e s e t r a n s h e x a f l u o r o b u t e n y 1 d e r i v a t i v e s do n o t g i v e a d o u b l e b o n d a b s o r p t i o n i n t h e i n f r a r e d s p e c t r a . T h i s a p p e a r s t o i n d i c a t e t h a t t h e d i p o l e moment o f t h e C - H b o n d i s t h e same a s t h a t o f t h e M - C (M = S i , G e , Sn) b o n d a n d t h a t t h e e l e c t r o n e g a t i v i t i e s o f S i , Ge a n d S n a r e a l m o s t i d e n t i c a l . T h e e l e c t r o n e g a t i v i t i e s o f t h e s e t h r e e e l e m e n t s h a s b e e n c a l c u l a t e d t o be v e r y s i m i l a r i n a n u m b e r 1 "39 o f i n v e s t i g a t i o n s ^ . T A B L E V I I SOME C H A R A C T E R I S T I C I N F R A R E D A B S O R P T I O N S • O F THE 1, 1, 1,1+, !+,'!+- H E X A F LUOR OBUT ENY L D E R I V A T I V E S a X C ( C F )=CHCF •X - C - F s t r e t c h i n g ( C H 3 ) 3 S i 1351+ s 1300 m 1257 v s 111+1 v s b ( C 2 H 5 ) 3 G e 131+1 s 1293 m 1257 v s 111+2 v s 850 c m ( C H 3 ) 3 S n 1328 s 1291 m 1255 v s 111+0 v s 81+9 rv, C m ( C 2 H 5 ) . jSn 1328 s 1292 m 1255 v s 1139 v s 850 c m ( C u H 9 ) 3 S n 1330 s 1295 m 1255 v s 111+3 v s 850 m c (C, H ) S n d 1+9 2 1329 s 1295 m 1255 v s 1139 v s 850 m c 3. L i q u i d f i l m . _j . • H i d d e n by : (CH ) S i r o c k i n g a b s o r p t i o n a t 81+9 cm . ' ^ C - H (-C=CH) 3 3 o u t o f p l a n e d e f o r m a t i o n . d ( C ^ H 9 ) 2 S n ( C ( C F 3 ) = C H C F 3 ) 2 A r e a c t i o n b e t w e e n t r i e t h y 1germahe a n d h e x a f l u o r o b u t - 2 - y n e d o e s n o t o c c u r i n t h e d a r k a t 20° b u t g i v e ^ t h e 1:1 a d d u c t , 1 , 1 , 1 , l + , l + , l + - h e x a f l u o r o b u t e n y l t r i e t h y l g e r m a n e , b . p . 82° (26 mm), u p o n u l t r a v i o l e t i r r a d i a t i o n . The p r o d u c t i s i d e n t i f i e d by i t s i n f r a r e d 97 s p e c t r u m ( T a b l e V I I ) a n d i t s * H n . m . r . s p e c t r u m ( T a b l e V I ) . T h e r e a c t i o n o f t r i m e t h y l s i l a n e a n d - h e x a f l u o r o b u t - 2 - y n e u n d e r t h e i n f l u e n c e o f u l t r a v i o l e t l i g h t a f f o r d s b o t h t h e 1:1 a d d u c t , 1 , 1 , 1 , k , k , k - h e x a f l u o r o b u t e n y l t r i m e t h y l s i l a n e , b . p . 98 (75k mm), a n d t h e 1:2 a d d u c t , 1 , 1 , 1 , k , k , k - h e x a f l u o r o b u t e n e - 2 , 3 ~ b i s ( t r i m e t h y 1 -s i l a n e ) , b . p . 79 (38 mm). ( C H ^ S i H +• C F ^ C z C C F ^ ( C H 3 ) 3 S i C ( G F 3 ) = C H C F 3 + ( C H 3 ) 3 S i C H ( C F 3 ) C H ( C F 3 ) S i ( C H 3 ) 3 The 1:1 a d d u c t i s i d e n t i f i e d b y i t s i n f r a r e d s p e c t r u m ( T a b l e V I I ) a n d i t s n . m . r . s p e c t r u m ( T a b l e V I ) . T h e 1:2 a d d u c t i s i d e n t -i f i e d by i t s * H n . m . r . s p e c t r u m o f a b r o a d m e t h y l a b s o r p t i o n a t 0 . 1 0 p . p . m . a n d a m u l t i p l . e t a't - 1 . 6 6 p . p . m . ( r e l a t i v e i n t e n s i t y 19 9 . 0 : 1 ) , a n d by i t s F n . m . r . s p e c t r u m ' o f b r o a d d o u b l e t s o f e q u a l i n t e n s i t y a t - 2 1 . 8 p . p . m . ( J = 13 c p s ) a n d - 2 3 . 6 p . p . m . ( J = 12 19 c p s ) . T h e F n . m . r . s p e c t r u m c a n be e x p l a i n e d o n t h e b a s i s o f a 1:1 m i x t u r e o f t h e m e s o - a n d r a c e m i c d , 1 i s o m e r s o f t h e f o l l o w i n g s t r u c t u r e s . (CH3)3Si ( C H 3 ) 3 meso d , l T h e c o u p l i n g o f 12 a n d 13 c p s c a n be a s s i g n e d t o t h e g e m i n a l C F . J - H c o u p l i n g a n d t h e b r o a d e n i n g a s s i g n e d t o t h e v i c i n a l C F ^ C F a n d C F 3 ~ H c o u p l i n g s . T h e t w o s k e w c o n f o r m a t i o n s s h o w n a b o v e w o u l d 98 probably be the h i g h e s t populated conformations of each s t r u c t u r e because of s t e r i c c o n s i d e r a t i o n s . I f the diadduct were the un-symmetrical 2 , 2 - b i s ( t r imethy 1 s i l y l ) butane, ( ( C r L ^ S i ) ( C F 3 ) O ^ ^ y 19 then the F n.m.r. s p e c t r a would c o n s i s t of a broad- s i n g l e t and a t r i p l e t . T h i s i s not found. The r a t i o of the 1:1 adckict, 1, 1, 1, l | , 1+, 1+-hexaf luorobuteny 1-t r i m e t h y l s i l a n e , to the 1:2 adduct i n the product can be v a r i e d by v a r y i n g the r a t i o of the r e a c t a n t s as shown i n Table V I I I . It i s r e a d i l y seen that the r a t i o of the 1:1 adduct to the 1:2 adddct decreases as the r a t i o of t r i m e t h y l s i l a n e to butyne i n c r e a s e s . To check i f the diadduct forms by the a d d i t i o n of butyne to the 1:1 adduct a mixture of the two r e a c t a n t s were i r r a d i a t e d . It i s found that a d d i t i o n of t r i m e t h y l s i l a n e to the 1:1 adduct gives only a low y i e l d of the diadduct (Table VIII) ( C H 3 ) 3 S i H + ( C H 3 ) 3 S i C ( C F 3 ) = C H C F 3 I ( C H ^ 3 S i ( C F^CH i_ The a d d i t i o n of t r i m e t h y l s i l a n e to hexafluorobut - 2-yne to give the mono- 'and diadduct a l s o occurs upon h e a t i n g . The r e s u l t s of t h i s r e a c t i o n are a l s o t a b u l a t e d i n Table V I I I . TABLE VIII FORMATION OF 1:1 AND 1:2 TRIMETHYLSILANE-BUTYNE ADDUCTS (1) R e a c t i o n of T r i m e t h y l s i l a n e and Hexafluorobut - 2-yne m i l l i m o l e s r e a c t a n t r e a c t i o n m i l l i m o l e s product ( C H 3 ) 3 S i H CF 3C=CCF 3 c o n d i t i o n s 1:1 a d d u c t ( c i s : t r a n s ) a 1:2 adduct 28 6~9 \)V (11 days) 105 25 it 11 39 235° (7 nr.) 77 17 » (2) R e a c t i o n of T r i m e t h y l s i l a n e and t l ( C H ^ S i H 1: 1 adduct i+8 7-9 (trans) -. fyV (11 days) 45 12.8 (trans) 1 2 3 5 ° (7 nr.) a • l u 1 H n.m.r. a n a l y s i s . 2 1 . 6 ( 0 : 1 ) k.2 5-9 ( 0 : 1) 6 . 5 15-0 ( 0 : 1) 6 . 5 7-3 (1 :15) -12.5 ( 1 :10) 1: 1 Adduct 7 . 0 ( 0 : 1 ) 0 . 8 12.5 ( 1 : 6 ) -99 T h e r e a c t i o n o f e x c e s s b u t y n e w i t h t r i m e t h y l s i l a n e g i v e s a f r a c -t i o n o f l o w v o l a t i l i t y w h i c h c o n t a i n s n i n e c o m p o n e n t s ( v . p . c . a n a l y s i s ) a n d i t s i n f r a r e d s p e c t r u m i n d i c a t e s t h a t l i t t l e o r no d i a d d u c t i s f o r m e d . E x c e s s t r i m e t h y l s i l a n e a n d t h e b u t y n e w h e n h e a t e d t o 235° . g i v e , - a 26% y i e l d o f 1:1 a d d u c t , a n 18% y i e l d o f d i a d d u c t a n d a kk% y i e l d o f t e t r a m e t h y l s i l a n e . ( C H 3 ) 3 S i H + C F 3 C E C C F 3 (CH^)^SiC(CF3)=CHCF3 + ( C H 3 ) L S i + ( ( C H 3 ) 3 S i C ( G F 3 ) H ) 2 I n v i e w o f t h e h i g h y i e l d o f t e t r a m e t h y l s i l a n e a n d t h e l o w y i e l d o f t h e d i a d d u c t i t was t h o u g h t t h a t t h e d i a d d u c t m i g h t s l o w l y d e c -o o c o m p o s e a t 235 • H o w e v e r , a f t e r s e v e n h o u r s a t 235 t h e d i a d d u c t i s q u a n t i t a t i v e l y r e c o v e r e d . The 1:1 a d d u c t f r o m t h e i r r a d i a t e d r e a c t i o n s i s 100% t r a n s - i s o m e r w h e r e a s t h e 1:1 a d d u c t f r o m t h e t h e r m a l r e a c t i o n s h a s a c i _ s - i s o m e r c o n c e n t r a t i o n w h i c h v a r i e s f r o m 6 t o A l t h o u g h n o m e a s u r a b l e a d d i t i o n o f t r i m e t h y l s i l a n e t o t h e t r a n s 1:1 a d d u c t o c c u r s a f t e r s e v e n h o u r s a t 235° i t i s f o u n d t h a t t h e c i s - i s o m e r c o n c e n t r a t i o n i n c r e a s e s t o l k % . C F , , , CF C F ( C ! - ! , ) 3 S i M C=Cy - > C~C + (CH3)3SiH + C — C. (CH 3 ) 3 Si / X C F 5 H o w e v e r , i f t h e t r a n s 1:1 a d d u c t I s h e a t e d a l o n e , t h e n c o n v e r s i o n t o t h e c 1 s - i s o m e r d o e s n o t o c c u r . .The 1:1 a d d u c t i s a l s o u n a f -f e c t e d b y u l t r a v i o l e t l i g h t e v e n i n t h e p r e s e n c e o f t r i m e t h y l -s i l a n e o r h e x a f l u o r o b u t - 2 - y n e . . . I t was o r i g i n a l l y t h o u g h t t h a t b e c a u s e o f t h e p o l a r i t y o f t h e 100 t i n h y d r i d e b o n d ( S n - H ) a n d t h e p o l a r i t y o f t h e a c e t y l e n i c c a r b o n h y d r o g e n b o n d ( C E C - H ) t h a t t h e r e a c t i o n o f 1 , 1 , 1 - t r i f l u o r o p r o p y n e w i t h t r i m e t h y l t i n h y d r i d e m i g h t p r o d u c e h y d r o g e n a n d t h e p r o p y n -y l t i n d e r i v a t i v e , ( C H ^ ) ^ S n C E C C F ^ , b u t t h i s d o e s n o t o c c u r . T h e r e a c t i o n b e t w e e n t r i m e t h y l t i n h y d r i d e a n d t h e p r o p y n e a t 20° i s s i m i l a r t o t h e ' t r i m e t h y l s i l a n e - h e x a f l u o r o b u t - 2 - y n e r e a c t i o n d e s -c r i b e d a b o v e i n t h a t b o t h 1:1 a n d 1:2 a d d u c t s a r e p r o d u c e d . ( C H ^ S n H + HC'ECCF * (CH^) 3 S n C H = C H C F 3 + ( C H 3 ) 3 S n C ( C F 3 ) = C H 2 + ( ( C H 3 ) 3 S n ) 2 C H G H 2 C F 3 T h e 1:1 a d d u c t i s i d e n t i f i e d by i t s * H n . m . r . s p e c t r u m o f m e t h y l a b s o r p t i o n s a t - 0 . 0 5 a n d 0 . 0 0 p . p . m . , f o u r d o w n f i e l d q u a r t -e t s , t w o c e n t r e d a t - 5 . 8 2 p . p . m . a n d t w o c e n t r e d a t - 6 . 8 1 p . p . m . , w h i c h a r e a s s i g n e d t o t h e t r a n s - i s o m e r , a n d a d o u b l e t a t -5.1+8 p . p . m . a n d t w o q u a r t e t s a t - 6 . 1 8 p . p . m . w h i c h a r e a s s i g n e d t o t h e i s o - i s o m e r . T h e r e l a t i v e i n t e n s i t y o f t h e d o w n f i e l d a b s o r p t i o n s t o t h e m e t h y l a b s o r p t i o n s i s 2 : 9 - 2 . F i g u r e 5 s h o w s t h e * H n . m . r . s p e c t r u m a n d - t h e a s s i g n m e n t s o f t h e c h e m i c a l s h i f t s a n d c o u p l i n g c o n s t a n t s f o r t h e t r a n s - a n d i s o - i s o m e r s'. I t a p p e a r s t h a t t h e r e m a i n i n g d o w n f i e l d o l e f i n i c p e a k s may be a s s i g n e d t o t h e c i s -i s o m e r i f J i s o f t h e same o r d e r a s t h e c h e m i c a l s h i f t b e t w e e n HH t h e s e p r o t o n s . T h i s s i t u a t i o n w o u l d g i v e l a r g e s e c o n d o r d e r e f -f e c t s . On t h e b a s i s o f t h e * H n . m . r . s p e c t r u m t h e 1:1 a d d u c t a n -a l y z e s t o be 65% t r a n s - , 13% c i s - a n d 22% i s o - i s o m e r . T h i s i s o m e r d i s t r i b u t i o n d o e s n o t m e a s u r a b l y a l t e r a f t e r d i s t i l l a t i o n o f t h e 1:1 a d d u c t . 1 F i g u r e 6 g i v e s t h e H n . m . r . s p e c t r u m o f t h e 1:1 d i m e t h y l a r -126 s i n e - 1 , 1 , 1 - t r i f l u o r o p r o p y n e a d d u c t s . A c o m p a r i s o n o f F i g u r e 5 w i t h F i g u r e 6 s h o w s t h e s i m i l a r i t y o f t h e s p e c t r a o f t h e r e s p -e c t i v e t r a n s - i s o m e r s . T h e H - H c o u p l i n g c o n s t a n t o f t h e i s o - a r s i n e 101 i s o m e r i s n e g l i g i b l e w h e r e a s t h a t o f t h e i s o - t i r i i s o m e r i s 1.5 c p s b u t b e y o n d t h i s t h e s i m i l a r i t y o f t h e r e s p e c t i v e i s o - i s o m e r s i s r e a d i l y a p p a r e n t . T h e 1:2 a d d u c t , ( ( C H ^ ) ^ S n ) ^ C H C H ^ C F ^ , i s i d e n t i f i e d by i t s *H n . m . r . s p e c t r u m o f one m e t h y l a b s o r p t i o n a t - 0 . 2 0 p . p . m . a n d a m e t h y l e n e a b s o r p t i o n a t - 2 . 5 8 p . p . m . c o n s i s t i n g o f t w o q u a r t e t s w i t h v i c i n a l H - H c o u p l i n g o f 8 . 0 c p s a n d g e m i n a l C F ^ - H c o u p l i n g o f 10 .5 c p s . T h e r e l a t i v e i n t e n s i t y o f t h e m e t h y l e n e a b s o r p t i o n t o t h e m e t h y l a b s o r p t i o n i s 1:10. T h e m e t h i n e a b s o r p t i o n i s p r o b -a b l y o b s c u r r e d b y t h e t i n m e t h y l si'^ dfe b a n d s s i n c e i t w o u l d be e x -p e c t e d t o be a t h i g h e r f i e l d t h a n t h e m e t h y l e n e a b s o r p t i o n . T h e 1 , 2 - t r i m e t h y l t i n a d d u c t , ( C H ^ ) ^ S n C H C C F ^ ) C H ^ n i C H ^ ) y w o u l d be e x -p e c t e d t o show t w o m e t h y l a b s o r p t i o n s a n d t h e m e t h y l e n e a b s o r p -t i o n w o u l d be e x p e c t e d t o show t w o q u a r t e t s w i t h J . . ' " ' 8 c p s a n d n r i J C F 3 H ~ 2 C P S ' The- r a t i o o f m o n o a d d u c t t o d i a d d u c t v a r i e s w i t h t h e t r i m e t h y l -t i n h y d r i d e - p r o p y n e r a t i o a s i n d i c a t e d i n T a b l e I X . T A B L E I X R E A C T I O N OF T R I M E T H Y L T I N H Y D R I D E AND 1 , 1 , 1 - T R I F L U O R O P R O P Y N E m i l l i m o l e s r e a c t a n t s r e a c t i o n m i l l i m o l e s p r o d u c t s r a t i o r a t i o ( C H ^ ) ^ S n H C F ^ C E C H c o n d i t i o n s 1:1 a d d u c t 1:2 a d d u c t 35 1+9 1:1.1+ 20° (1 d a y ) 15 5-7 2 . 6 : 1 12 11 1 : 0 . 9 20° (1+ d a y s ) 1+.2 2.1+ 1 .8:1 T h e d i a d d u c t i s n o t p r o d u c e d w h e n t r i m e t h y l t i n h y d r i d e a n d t h e 1:1 a d d u c t a r e l e f t f o r t w o d a y s a t 20° a l t h o u g h t h e c i s - i s ome r c o n c e n t r a t i o n o f t h e 1:1 a d d u c t d e c r e a s e s f r o m 13 t o Q%. C=C\ +(CH,VSnH >/ N C - C " C S K^SnH + H H V 3» (CH^Sn H H A \ .m.r.. S p e c t r u m o f 1:1 T r i m e t h y l t i n H y d r i d e - 1 , 1 , . 1 - T r i f l u o r o p r o p y n e A d d u c t s F i g u r e 6: (a) 103 n . m . r . S p e c t r u m o f 1:1 . D i m e t h y l a r s i n e - • 1 , 1 , i - T r i f l u o r o p r o p y n e A d d u c t s 1 j] 3.5 L— 4.5 (b) 1—13- lC=C\ /cp* cps 3.35 3.56 4.10 (c) I-—18-299 3.27 y 8 l a H, M e 2 A s , 8 -C F - ^ S — i s — I -2-cps 4.22 4.51 (d) 4.05 H. 4.55 T 101+ The isomer d i s t r i b u t i o n of the 1:1 adduct from the r e a c t i o n of dimethylamine and 1 , 1 , 1 - t r i f l u o r o p r o p y n e i s s t r i k i n g l y d i f f e r -ent from the isomer d i s t r i b u t i o n of the 1:1 adduct obtained from the r e a c t i o n of the same a c e t y l e n e with d i m e t h y l a r s i n e or t r i -m e t h y l t i n h y d r i d e . The 1:1 adduct, 3 ~ d i m e t h y l a m i n o - 1 , 1 , 1 - t r i -fluoropropene, b.p. 1 1 8 ° (759 mm), i s obtained i n 57% y i e l d from the r e a c t i o n , of the amine and the propyne. C F ^ E C H + (CH 3) 2NH > CF 3CH^=CH XN(CH 3) 2 T h i s 1:1 adduct can be assigned the trans c o n f i g u r a t i o n from a comparison of i t s *H n.m.r. spectrum with F i g u r e 6 . Two q u a r t e t s at - 6 . 1 7 p.p.m. with = 13 cps and J ^ p u = 1.5 cps can be as-3 signed to and the o v e r l a p p i n g q u a r t e t s at - 3 . 6 6 p.p.m. with J Q P J_, = 6 . 5 cps can be assigned to H p . The r e l a t i v e i n t e n s i t y of the o l e f i n i c protons to the methyl peak i s 1:3«. I t s i n f r a r e d spec-trum shows strong bands at 96O and 1307 cm * which can be assigned to the t r a n s -HG=CH- " o u t - o f - p l a n e " and " i n - p l a n e " bending v i b - a 133 1 r a t i o n s r e s p e c t i v e l y . The ( H n.m.r. spectrum shows no s i g n s of any other isomer. The t r a n s - 1 - d i m e t h y l a m i n o - 3 , 3 « 3 ~ t r i f l u o r o -propene i s u n s t a b l e to d i s t i l l a t i o n (76O mm), although the isomer d i s t r i b u t i o n i n the undecomposed d i s t i l l a t e remains unchanged. (2) Proposed Mechanism of H y d r i d e - F l u o r o a c e t y l e n e Reactions (a) T i n H y d r i d e s i - - F u l t o n * ^ ) found that t i n h y d r i d e s add t r a n s to p h e n y l a c e t y l e n e to give the c i s - i somer which rearranges on warming to the more s t a b l e t r a n s - i s o m e r . H /CfcHy c—c (CH3)3Srv/ N H io5 T h e p r e s e n c e o f a n y i s o - i s o m e r was n o t o b s e r v e d by F u l t o n . T h e r e a c t i o n o f t r i m e t h y l t i n h y d r i d e a n d m e t h y l a c e t y l e n e i s r e p o r t e d t o g i v e a l l t h r e e i s o m e r s , t r a n s - , c i s - a n d i s o p r o p e n y l t r i m e t h y l -t i n i n a r a t i o o f 6 8 : 2 8 : ( C H ^ S n H + H C E C C H ^ ( C H ^ S n O ^ C H C H ^ + (CH^) ^SnC (CH^) =C I n t h e p r e s e n t i n v e s t i g a t i o n t h e r e a c t i o n o f t i n h y d r i d e s w i t h h e x a f l u o r o b u t - 2 - y n e p r o d u c e s a l m o s t c o m p l e t e l y t r a n s - i s o m e r ( T a b l e V I ) . A . f o u r - c e n t r e m e c h a n i s m , a s s h o w n , w o u l d n o t a c c o u n t f o r p r e d o m -i n a n c e o f t h e t r a n s - i s o m e r . C F - C = = C C F . R S n H + C F C E C C F *- 3 | J 3 i -* ~> R S n - - - H 3 T h e s p e e d o f t h i s r e a c t i o n i s . a l s o a g a i n s t s u c h a m e c h a n i s m s i n c e t h e o r i e n t a t i o n n e c e s s a r y f o r a f o u r - c e n t r e a d d i t i o n i s n o t e x -p e c t e d t o a l l o w a r e a c t i o n t o be c o m p l e t e w i t h i n s e c o n d s . T h e r e a p p e a r t o be t w o r e a s o n a b l e m e c h a n i s m s i n v o l v i n g e i t h e r h y d r i d e n u c l e o p h i l i c a t t a c k o r t i n e l e c t r o p h i 1 i c a t t a c k o n t h e a c e t y l e n e . A g e n e r a l r u l e o f t r a n s n u c l e o p h i l i c a d d i t i o n t o a l -k y n e s h a s b e e n p o s t u l a t e d 1 ^ " 2 . B u r n e l l e 1 ^ " 3 h a s a l s o c a l c u l a t e d t h a t a t r a n s d i s t o r t i o n o f t h e a l k y n e i s t o be e x p e c t e d o n t h e a p p r o a c h o f a n e l e c t r o p h i l e , t h u s l e a d i n g t o t r a n s e l e c t r o p h i 1 i c a d d i t i o n s . T h e s p e e d o f t h e t i n h y d r i d e - h e x a f l u o r o b u t - 2 - y n e r e a c -t i o n i n w h i c h t h e a c e t y l e n e c a r b o n a t o m s h a v e t h e h i g h l y e l e c t r o n w i t h d r a w i n g - C F ^ g r o u p s a t t a c h e d , a n d t h e s l o w n e s s o f t h e t i n h y -d r i d e - m e t h y l a c e t y l e n e r e a c t i o n w h i c h i s o n l y 30% c o m p l e t e a f t e r e i g h t e e n h o u r s a t 100° 1 ^ ' 1 i n d i c a t e n u c l e o p h i l i c a t t a c k . H a s -122 z e l d i n e f o u n d t h a t h e x a f l u o r o b u t - 2 - y n e i s v e r y s u s c e p t i b l e t o n u c l e o p h i l i c a t t a c k b u t r e q u i r e s c a t a l y s t s t o r e a c t w i t h e l e c t r o -p h i l i e r e a g e n t s . The r e a c t i o n o f 1 , 1 , 1 - t r i f l u o r o p r o p y n e a n d t r i m e t h y l t i n h y d r i d e 106 i s 80% complete a f t e r four days at.2 0 ° and give s predominantly the t r a n s 1:1 adduct. The major product can be ex p l a i n e d by the f o l l o w i n g f o u r - c e n t r e a d d i t i o n . CF-C^ CH X:F.K M CF,C=CH + (CH-)-SnH—J-* J i ,' J)C=C •> * * H---Sn(CH3)3 * H N S n ( C H 3 ) 3 However, an a l t e r n a t e mechanism to account f o r t r a n s - 1 , 1 , 1 - t r i -f l u o r o p r o p e n y l - 3 - t r i m e t h y l t i n i n v o l v e s t r a n s n u c l e o p h i l i c a d d i t i o n to give the c i s - i somer f o l l o w e d by i s o m e r i z a t i o n . F u l t o n 1 ^ des-c r i b e s the t r i m e t h y l t i n hydride c a t a l y z e d i s o m e r i z a t i o n of c i s- ft -s t y r y l t r i m e t h y l t i n to the t r a n s - i somer •> In the present i n v e s t -i g a t i o n there was t i n hydride remaining i n the propyne-trimethy 1 -t i n h y d r i d e r e a c t i o n consequently a s i m i l a r r e s u l t might be ant-i c i p a t e d . Ihcbeed i t i s found t r i m e t h y l t i n hydride does c a t a l y z e the i s o m e r i z a t i o n of c l s - 1 , 1 , 1 - t r i f l u o r o p r o p e n y 1 - 3 - t r i m e t h y l t i n 122 to the t r a n s - i somer. Haszeldine found that both e l e c t r o p h i 1 i c and n u c l e o p h i l i c reagents a d d . r e a d i l y to 1 , 1 , 1 - t r i f l u o r o p r o p y n e ; e l e c t r o p h i l e s a t t a c k at the c e n t r a l carbon and n u c l e o p h i l e s a t t a c k at the t e r m i n a l a c e t y l e n i c carbon. On t h i s b a s i s e l e c t r o p h i 1 i c a t t a c k by the t i n atom of t r i m e t h y l t i n hydride and n u c l e o p h i l i c a t t a c k by the hydride group on t r i m e t h y l t i n hydride would give the i s o - i stmie r, v i z . 1 / nuc 1 eophi l i e a t t a c k : Qp^-C = C > C—Cf C F 3 C E C H + ( C H 3 ) 3 S n H — 3 CF^ N H + , s Q H (CM)Sn ,1-1 +(CH,),S. fcHlSnM-+ f=C' —> 3 3 ) C = C / H + H" ° CF 3 X H ' CFS N H e l e c t r o p h i l i e a t t a c k : QJ— C F 3 C E C H + (CH 3) 3SnH 3 XC3C X U — \ > C X l J + H n 107 C E (CH3).. \ + Cn H + C=C +(CH,),SnH • \=C( + (CH,).,Sn U&T ^ ' M ( C H ^ ~ I n b o t h t h e r e a c t i o n s c h e m e s d e s c r i b e d a b o v e a s e c o n d t r i m e t h y l t i n h y d r i d e m o l e c u l e m i g h t n o t be i n v o l v e d , t h e r e a c t i o n m e c h a n i s m p r o b a b l y b e i n g m o r e c o n c e r t e d t h a n i s i n d i c a t e d . C u l l e n a n d Daw-126 s o n • o b s e r v e d t h a t t h e r e a c t i o n o f 1 , 1 , 1 - t r i f l u o r o p r o p y n e a n d d i m e t h y l a r s i n e g i v e s a 30% y i e l d o f . t h e i s o - i s o m e r , t h e r e m a i n i n g 1:1 a d d u c t (70%) b e i n g a m i x t u r e o f c i s - a n d t r a n s - 3 - d i m e t h y l a r -s i n o - 1 , 1 , 1 - t r i f l u o r o p r o p e n e . S i n c e t h e m e c h a n i s m o f f o r m a t i o n o f t h e .1:1 a r s i n e - p r o p y n e a d d u c t p r o b a b l y i n v o l v e s n u c l e o p h i l i c a t -t a c k by t h e a r s e n i c l o n e p a i r i t a p p e a r s t h a t n u c l e o p h i l i c a t t a c k c a n o c c u r a t t h e c e n t r a l c a r b o n a t o m o f 1 , 1 , 1 - t r i f l u o r o p r o p y n e . C F © ( C H O o A s H + C F ^ C E C H • ">C=C 3 d 3 ( C H ) A s X H /} 3 2 + H C F / G 3 "X*=C • (CH ) A s C ( C F j = C H 0 ( i s o i s o m e r , 30%) ( e H 3 ' 2 A / A " H 3 3 T h u s , f r o m t h e a r s i n e - p r o p y n e r e s u l t s a s i m i l a r n u c l e o p h i l i c a t -t a c k w o u l d e x p l a i n t h e f o r m a t i o n o f t r a n s - 1 , 1 , 1 - t r i f l u o r o p r o p e n y 1-t r i m e t h y l t i n . C F . r * ( C H - ) . S n H + C F . C E C H » J „ C E C ^ H • 3 3 3 ( C H 3 ) 3 S n ^ H H -C F 3 ^ _ 0 / C—C-^j^ H ® S n ( C H 3 ) 3 J C F , . / S n ( C H . ) -H H T h e r e a c t i o n o f 1 , 1 , 1 - t r i f l u o r o p r o p y n e a n d t r i m e t h y l t i n h y -d r i d e a l s o g i v e s a c o n s i d e r a b l e y i e l d o f t h e d i a d d u c t , 1 , 1 , 1 - t r i -f l u o r o - 3 , 3 - b i s ( t r i m e t h y 1 s t a n n y 1 ) p r o p a n e . S i n c e t h e t i n h y d r i d e d o e s n o t a d d t o t h e 1:1 a d d u c t a t 20° i n t h e d a r k i t seems t h a t 108 t h e m e c h a n i s m t o f o r m t h e d i a d d u c t i s c o n c e r t e d . I f t h e p o s t u l -a t e d i n t e r m e d i a t e f o r t h e f o r m a t i o n o f t h e 1:1 a d d u c t , C F 3 C H = C H , h a s a f i n i t e l i f e t i m e t h e n i t seems p r o b a b l e t h a t a s e c o n d t r i -m e t h y l t i n h y d r i d e m o l e c u l e c o u l d be a t t a c k e d . 3'3 (CHlSnH-CFf^- C(H)Sn(Cfi), +Sr.,(CH,)/": CF£H=CH CF,CWXH'fSnfcHj,), 122 H a s z e l d i n e o b t a i n e d some 2 , 2 - d i a l k o x y b u t a n e f r o m t h e b a s e c a t -a l y z e d r e a c t i o n o f h e x a f l u o r o b u t - 2 - r y n e a n d a l c o h o l s a t 0° a n d o b -s e r v e d t h a t a s e c o n d m o l e o f a l c o h o l d o e s n o t a d d t o t h e m o n o -a l k o x y b u t e n e u n d e r t h e same c o n d i t i o n s . ( b ) S i l a n e s a n d G e r m a n e s - - T h e u l t r a v i o l e t i n i t i a t e d r e a c t i o n s o f t r i m e t h y l s i l a n e a n d t r i e t h y l g e r m a n e w i t h h e x a f l u o r o b u t - 2 - y n e a l s o a f f o r d t h e 1:1 a d d u c t o f p r e d o m i n a n t l y t r a n s c o n f i g u r a t i o n ( T a b l e V I ) . T h i s m i g h t be e x p e c t e d s i n c e a c e t y l e n e i s t r a n s b e n t i n i t s f i r s t s i n g l e t e x c i t e d s t a t e 1 ^ " 3 . H o w e v e r , a r a t h e r b e w i l d -e r i n g p o i n t i s t h a t a b o v e 300.0 A t h e r e d o e s n o t a p p e a r t o be a n y u l t r a v i o l e t a b s o r p t i o n by h e x a f l u o r o b u t - 2 - y n e . N e v e r t h e l e s s i n t h i c k - w a l l e d P y r e x t u b e s , w h i c h do n o t t r a n s m i t a n y s i g n i f i c a n t c a m o u n t o f l i g h t b e l o w 3000 A , t h e r e a c t i o n s do p r o c e e d u p o n i r -r a d i a t i o n t o g i v e t h e 1:1 t r a n s a d d i t i o n p r o d u c t s . A s s u m i n g t h a t t h e b u t y n e d o e s a b s o r b some r a d i a t i o n t o g i v e a s i n g l e t e x c i t e d s t a t e i t seems p r o b a b l e t h a t o n c o l l i s i o n t h e e x c i t e d b u t y n e c o u l d f a l l t o a l o w e r l y i n g t r i p l e t s t a t e a n d c o m b i n e w i t h a t r i m e t h y l -s i l a n e o r t r i e t h y l g e r m a n e m o l e c u l e t o g i v e a r a d i c a l i n t e r m e d i a t e . 109 C F o C E C C F G F 0 C = C C F 3 C F . C E C C F . " " " + (CH_) , S i H (CHISITH XCF 3 T h i s i n t e r m e d i a t e c o u l d t h e n f o r m t h e 1:1 a d d u c t by i n t r a m o l e c u l a r o r i n t e r m o l e c u l a r p r o t o n a b s t r a c t i o n . I n t h e t h e r m a l r e a c t i o n o f t r i m e t h y l s i l a n e a n d h e x a f l u o r o b u t -2 - y n e , s i n c e t r i m e t h y l s i l a n e c a t a l y z e s t h e i s o m e r i z a t i o n o f t h e t r a n s 1:1 a d d u c t t o t h e c i s - i s o m e r , t h e i s o m e r d i s t r i b u t i o n o f t h e 1:1 a d d u c t c h a n g e s w i t h t h e c o n c e n t r a t i o n o f t r i m e t h y l s i l a n e a n d d u r a t i o n o f h e a t i n g . I t seems p r o b a b l e t h a t t h e i n i t i a l r e a c -t i o n i n v o l v e s a t r a n s n u c l e o p h i . l i c a d d i t i o n s i m i l a r t o t h a t p o s -t u l a t e d f o r t h e f o r m a t i o n o f t h e 1:1 t i n h y , d r i d e - b u t y n e a d d u c t s . H o w e v e r a r a d i c a l m e c h a n i s m c a n n o t be d i s r e g a r d e d e s p e c i a l l y i n v i e w o f t h e h i g h y i e l d o f t e t r a m e t h y I s i l a n e (kk%) i n t h e b u t y n e -e x c e s s t r i m e t h y l s i l a n e r e a c t i o n . T h e s y m m e t r i c a l b u t e n e - 2 , 3 ~ b i s t r i m e t h y 1 s i l a n e i s o b t a i n e d f r o m t h e t r i m e t h y 1 s i l a n e - h e x a f l u o r o b u t - 2 - y n e r e a c t i o n b o t h o n h e a t i n g a n d i r r a d i a t i o n . I f t h e s i l a n e - h e x a f l u o r o b u t - 2 - y n e r a d -i c a l i n t e r m e d i a t e , (CH^) ^ S i ( H ' ) C ( C F 3 ) = C C F , p o s t u l a t e d a b o v e h a s a f i n i t e l i f e t i m e t h e n i t seems p r o b a b l e t h a t a n o t h e r s i l i c o n a t o m o n a s e c o n d t r i m e t h y l s i l a n e m o l e c u l e c o u l d be a t t a c k e d . T h i s s e c o n d i n t e r m e d i a t e ' c o u l d t h e n a f f o r d t h e d i a d d u c t b y i n t r a -m o l e c u l a r p r o t o n t r a n s f e r . A n o t h e r p o s s i b i l i t y w h i c h w o u l d a c -c o u n t f o r t h e d i a d d u c t f o r m a t i o n w o u l d i n v o l v e e n e r g y t r a n s f e r 110 by t h e b u t y n e t o t h e 1:1 a c k i u c t as-'.f o l l o w s : ( C H 3 ) 3 S i C ( G F 3 ) = C H C F 3 + C F ^ C i C C F ^ " * , C F 3 C = C C F 3 +. ( C H 3 ) 3 S i C ( G F 3 ) = C H C F 3 " " T h e e x c i t e d 1:1 a d d u c t c o u l d a d d t o a s e c o n d s i l a n e m o l e c u l e . I t i s n e c e s s a r y t o p o s t u l a t e t h e e x c i t e d 1:1 a d d u c t b e f o r e a s -s u m i n g a d d i t i o n s i n c e t h e e x p e r i m e n t a l r e s u l t s o f t h i s i n v e s t -i g a t i o n h a v e e s t a b l i s h e d t h a t t h e 1:1 a d d u c t d o e s n o t a d d a p p r e -c i a b l y t o t r i m e t h y l s i l a n e u p o n i r r a d i a t i o n . ( C H 3 ) 3 S i H + ( C H 3 ) 3 S i C ( C F 3 ) = C H C F 3 ^ » l i t t l e r e a c t i o n T h e m a i n r e a c t i o n p r o d u c t f r o m t h e t h e r m a l r e a c t i o n o f t r i m e t h y l -s i l a n e a n d h e x a f l u o r o b u t - 2 - y n e i s t e t r a m e t h y 1 s i l a n e . T h i s s u g -g e s t s t h e p r e s e n c e o f t h e r a d i c a l ( C H 3 ) 3 S i * a n d t h i s r a d i c a l , i f f o r m e d , c o u l d a f f o r d t h e d i a d d u c t o n a t t a c k o f t h e 1:1 a d d u c t . (CH ) _ S i * + (CH ) _ S i C ( C F _ ) = C H C F _ * (CH ) S i C ( C F ) C H C F 3 3 3 3 3 3 3 3 * 3 ( 3 S I ( C H ) A c o n c e r t e d m e c h a n i s m i n v o l v i n g n u c l e o p h i l i c a t t a c k o n t h e a c e t y l -ene w o u l d p r o b a b l y a f f o r d t h e 2,2 - b i s t r i m e t h y l^si l a n e , ( ( C H ) S i ) ^ -C ( C F 3 ) C H 2 C F 3 , s i n c e t h e u n s y m m e t r i c a 1 d i a l k o x y b u t e n e , C F C (OR^CH^CF^, was o b t a i n e d f r o m t h e b a s e - c a t a l y z e d r e a c t i o n o f h e x a f l u o r o b u t - 2 -1 2 ? y n e a n d a l c o h o l . B e n k e s e r a n d c o w o r k e r s * ^ f o u n d t h a t a d i a d d u c t , i n a d d i t i o n t o t h e m o n o a d d u c t , f o r m s w h e n t r i c h l o r o s i l a n e i s r e a c t e d w i t h t -b u t y l a c e t y l e n e i n t h e ' p r e s e n c e o f b e n z o y l p e r o x i d e . I t was a l s o f o u n d t h a t t r i c h l o r o s i l a n e a d d s t o t h e c i s 1:1 t - b u t y l a c e t y l e n e -s i l a n e a d d u c t i n t h e p r e s e n c e o f b e n z o y l p e r o x i d e b u t n o t t o t h e t r a n s 1:1 a d d u c t . I n t h e p r e s e n t i n v e s t i g a t i o n , h o w e v e r , i t was f o u n d t h a t a l t h o u g h t r i m e t h y l s i l a n e c a t a l y z e s t h e c o n v e r s i o n o f t r a n s - t o c_i_s- isomer i t d o e s n o t a d d e v e n t o t h e c i s - b u t e n y l s i l a n e . B . M e t a l - M e t a l B o n d s I l l ( 1) R e s u l t s H e x a f - l u o r o b u t - 2 - y n e a n d t e t r a k i s ( t r i f l u o r o m e t h y 1 ) d i a r s i n e r e a c t o n u l t r a v i o l e t i r r a d i a t i o n t o g i v e t h e 1:1 a d d u c t , 2 , 3 _ b i s -( b i s t r i f l u o r o m e t h y l a r s i n o ) h e x a f l u o r o b u t - 2 - e n e , b . p . l £ 6 G (760 mm). ( C F 3 ) 2 A s A s ( C F 3 ) 2 + G F 3 C = G C F 3 * (CF^)gAsC(CF ) = C ( C F )As(CF ) 2 The a b s e n c e o f a n y a b s o r p t i o n i n t h e C=C s t r e t c h i n g r e g i o n i n d -i c a t e s t h a t t h e p r o d u c t i s m a i n l y t h e t r a n s - i s o m e r . T h e p r o d u c t i s i d e n t i f i e d b y e l e m e n t a 1 . a n a l y s i s . I t h a s b e e n r e p o r t e d t h a t t e t r a k i s ( t r i f l u o r o m e t h y 1 ) d i a r s i n e a n d t h e b u t y n e do n o t r e a c t a t 100° ^ a l t h o u g h t h e b u t y n e d o e s r e a c t w i t h t e t r a m e t h y l d i a r s i n e a t 20° t o g i v e a n a p p r o x i m a t e 1:1 m i x t u r e o f t h e c i s - a n d t r a n s - i s o m e r s o f ( C H 3 ) 2 A s C ( C F 3 ) = C ( C F 3 ) A s ( C H 3 ) 2 . Q u a l i t a t i v e b a s e h y d r o l y s i s o f 2 , 3 - b i s ( b i s t r i f l u o r o m e t h y l a r s i n o ) h e x a f l . u o r o b u t - 2 - e n e g i v e s t r i -f l u o r o m e t h a n e a n d o n l y t r a n s - 1 , 1, 1, k , k , k - h e x a f l u o r o b u t - 2 - e n e . ( C F 3 ) 2 A s C ( C F 3 ) = C ( C F 3 ) A s ( C F 3 ) 2 + H 2 0 Q H » C H F 3 + C F 3 C H = C H C F 3 ( t r a n s ) T h e b u t y n e a n d h e x a m e t h y l d i t i n r e a c t o n u l t r a v i o l e t i r r a d i a t i o n t o g i v e a 1:1 a d d u c t , h e x a f l u o r o - 2 , 3 ~ b i s ( t r i m e ' t h y l s t a n n y l ) b u t - 2 -e n e , b . p . 5 3 ° (10 3 mm), w h i c h i s r a t h e r u n s t a b l e i n a i r . ( C H 3 ) 3 S n S n ( C H 3 ) 3 + C F ^ i Q ^ * ( C H ^ ) ^ S n C ( C F ^ ) = C ( C F ^ ) S n ( C H ) ^ The a d d u c t i s i d e n t i f i e d by e l e m e n t a l a n a l y s i s . T h e * H n . m . r . s p e c t r u m o f t h i s d i t i n a d d u c t c o n s i s t s o f a s i n g l e m e t h y l p e a k w h i c h i s s p l i t i n t o a m u l t i p l e t w i t h J — 0 . 8 c p s . T h i s s p l i t t i n g 19 i s a s s i g n e d t o C F ^ C H i n t e r a c t i o n . I t s F n . m . r . s p e c t r u m c o n -s i s t s o f o n l y o n e b r o a d p e a k i n d i c a t i n g t h e p r e s e n c e o f o n l y o n e 19 i s o m e r . T h e b r o a d n e s s o f t h e s i n g l e l i n e i n t h e F n . m . r . s p e c -t r u m i s p r o b a b l y a c o n s e q u e n c e o f w e a k C H 3 ~ C F 3 c o u p l i n g w h i c h i s e x p e c t e d t o be o f t h e o r d e r o f 1 c p s 1 - ^ . T h e a b s e n c e o f a n y C=C s t r e t c h i n g f r e q u e n c y i n t h e i n f r a r e d s p e c t r u m s u g g e s t s t h a t t h e 112 d i t i n a d d u c t i s t h e t r a n s - i s o m e r . T h e u s e o f i n f r a r e d s p e c t r a f o r a s s i g n i n g s t r u c t u r e s o f . t h i s t y p e a p p e a r s t o be r e l i a b l e s i n c e t h e c o m p o u n d , ( C H ^ ) 2 A s S C ( C F ^ ) = C ( G F ^ ) S A s ( G H ^ ) 2 , w h i c h w i t h o u t d o u b t h a s t h e c i s - s t r u c t u r e , h a s a s t r o n g b a n d a t 1535 cm 1 T h e 1:1 m i x t u r e o f ( C H ^ ) 2 A s C ( C F ^ ) = C ( C F ^ ) A s ( C H ^ ) 2 h a s a w e a k b a n d a t 1570 cm 1 a n d w h e n i t s p r e p a r a t i o n i s c a r r i e d o u t w i t h t h e 1:1 c o m p l e x , ( C H ^ ) ^ A s • ( C F ^ ) 2 C O j t h e y i e l d o f c i s - i s o m e r i s v e r y much i n c r e a s e d w i t h a c o r r e s p o n d i n g i n c r e a s e i n t h e i n t e n s i t y o f t h e 1570 cm 1 b a n d ( s e e C h a p t e r I , p a g e 2 3 ) . The 1:1 d i t i n a d d u c t i s n o t o b t a i n e d on h e a t i n g h e x a m e t h y 1 d i -t i n a n d t h e b u t y n e ; t r i m e t h y l t i n f l u o r i d e was t h e o n l y t i n c o n -t a i n i n g r e a c t i o n p r o d u c t i s o l a t e d f r o m t h i s r e a c t i o n . ( C H ^ S n S n ( C H ) + C F C=CCF - ^ - » - ( C ^ ) S n F The 1:1 d i t i n a d d u c t d o e s d e c o m p o s e o n h e a t i n g t o t e t r a m e t h y I t i n , h e x a m e t h y l d i t i n , 1, 1, 1, k , k , k - h e x a f l u o r o b u t e n y l t r i m e t h y l t i n , . a n d n u m e r o u s o t h e r u n i d e n t i f i e d l i q u i d s a n d s o l i d s . ( C H 3 ) 3 S n C ( C F 3 ) = C ( C F 3 ) S n ( C H 3 ) 3 * ( C H ^ S n + ( C H 3 ) 6 S n 2 + • ( C H 3 ) 3 S n C ( C F 3 ) = C H C F 3 B a s e h y d r o l y s i s o f t h e d i t i n a d d u c t g i v e s a c i s - . t r a n s m i x t u r e o f 1 , 1 , 1 , k , k , k - h e x a f l u o r o b u t e n e ; t h u s , i ' t d o e s n o t a p p e a r t h a t t h e r e i s r e t e n t i o n o f c o n f i g u r a t i o n u p o n h y d r o l y s i s . A l t h o u g h t h e r e i s a r e a c t i o n b e t w e e n h e x a b u t y 1 d i t i n a n d h e x a -f l u o r . o b u t - 2 - y n e o n u l t r a v i o l e t i r r a d i a t i o n , i t i s r a t h e r c o m p -l i c a t e d . The o n l y p r o d u c t t h a t w a s i d e n t i f i e d i s d i b u t y l b i s ( 1 , 1 , 1 , k , k , k - h e x a f l u o r o b u t e n y 1 ) t i n , ( C ^ H ^ ) 2 S n ( C ( C F 3 ) = C ( C F 3 ) H ) 2 , b . p . 6 0 -63° ( 1 0 ~ 3 mm). T h i s h a s t h e same b o i l i n g p o i n t a s t h e d i a d d u c t f o r m e d f r o m d i b u t y l t i n d i h y d r i d e a n d t h e b u t y n e ( p a g e 95') , a l -t h o u g h t h e i n f r a r e d s p e c t r u m s h o w s some s l i g h t d i f f e r e n c e s i n t h e C=C s t r e t c h i n g r e g i o n w h i c h a r e p r o b a b l y due t o a d i f f e r e n c e i n 113 i s o m e r d i s t r i b u t i o n . I t s * H n . m . r . s p e c t r u m s h o w s a d o w n f i e l d q u a r t e t , J ~ 8 c p s , t y p i c a l o f t h e g r o u p - C ( C F 3 ) = C ( C F 3 ) H . O t h e r f r a c t i o n s i s o l a t e d f r o m t h e r e a c t i o n s u g g e s t t h e p r e s e n c e o f o t h e r c o m p o u n d s o f t h e t y p e ( C ^ ) n S n ( C ( C F 3 ) = C ( C F 3 ) H ) ^ _ n . I f i t i s a s -s u m e d , a n d i t a p p e a r s r e a s o n a b l e , t h a t t h e 1:1 a d d u c t i s o r i g i n -a l l y f o r m e d f o l l o w e d by d e c o m p o s i t i o n t h e n t h e p r e s e n c e o f t h e c o m p o u n d w i t h n = 3 c o u l d be e x p e c t e d i n v i e w o f t h e r e s u l t s f r o m t h e t h e r m a l d e c o m p o s i t i o n o f (CH^) 3 S n C ( C F 3 ) = C ( C F 3 ) S n ( C H . j ) ^ • I t was f o u n d t h a t h e x a e t h y l d i g e r m a n e i s s t a b l e t o h e x a f l u o r o -b u t - 2 - y n e o n u l t r a v i o l e t i r r a d i a t i o n . T h i s i s e x p e c t e d i n v i e w o f t h e i n c r e a s i n g M - M b o n d s t r e n g t h i n t h e c o m p o u n d s R^MMR^ a s t h e g r o u p i s a s c e n d e d . (2) P r o p o s e d M e c h a n i s m o f M e t a l - M e t a l A d d i t i o n t o H e x a f l u o r o b u t - 2 - y n e U l 122 T i n h y d r i d e s , t e t r a m e t h y l a r s i n e ^ a n d a m i n e s a d d v i g o r o u s l y t o h e x a f l u o r o b u t - 2 - y n e a t 2 0 ° , a n d i n t h e s e r e a c t i o n s t h e m o s t p r o b a b l e m e c h a n i s m i n v o l v e s n u c l e o p h i l i c a t t a c k o n t h e a c e t y l e n i c c a r b o n s o f t h e b u t y n e . F o r t h e ; r e a c t i o n s i n v o l v i n g t h e i r r a d -i a t i o n o f t h e b u t y n e a n d t e t r a k i s ( t r i f l u o r o m e t h y 1 ) d i a r s i n e o r t h e d i t i n c o m p o u n d s t h e same m e c h a n i s m i s v e r y u n l i k e l y . T e t r a -k i s ( t r i f l u o r o m e t h y 1) d i a r s i n e i s p r o b a b l y a w e a k n u c l e o p h i l e b e -c a u s e o f t h e i n d u c t i v e e f f e c t o f t h e t r i f l u o r o m e t h y 1 g r o u p s a n d i t i s . u n l i k e l y t h a t a n y n u c l e o p h i l i c c h a r a c t e r c a n be a t t r i b u t e d t o t h e t i n a t o m s o f t h e d i t i n c o m p o u n d s . T h e p r e d o m i n a n t f o r m -a t i o n o f t h e t r a n s - i s o m e r f o r t h e . a d d i t i o n o f h e x a f l u o r o b u t - 2 - y n e t o h e x a m e t h y l d i t i n a n d t h e d i a r s i n e i s c o n s i s t e n t w i t h t h e t r a n s a d d i t i o n o f t r i m e t h y l s i l a n e a n d t r i e t h y l g e r m a n e t o t h e b u t y n e o n i r r a d i a t i o n a n d t h e r e f o r e a m e c h a n i s m i n v o l v i n g a s i m i l a r i n t e r -m e d i a t e C F ^ C E C C F ^ V > C F ^ C s C C F ^ " ( e x c i t e d s i n g l e t ) Ilk CF ( C H 3 ) 3 S n S n ( C H 3 ) 3 + CF^CsCCF^""' 3 \ c=c (CH3)3 f o l l o w e d b y i n t r a m o l e c u l a r t r i m e t h y l t i n t r a n s f e r i s p r o p o s e d C F 3 Sn(ChlX W / \ CF, n 5 REFERENCES 1. K. ZIEGLER, H. GROSSMANN, H. KLEINER and O. SCHAEFER. Ann. 4 7 3 , 1 ( 1 9 2 9 ) . 2 . K. ZIEGLER and K. BAHR. Ber. £6> 171+0, 21+53 ( 1 9 2 3 ) . 3 . K. ZIEGLER and H. G. GELLERT. Ann.. £6_7_, 195 ( 1 9 5 0 ) . 1+. K. ZIEGLER. Angew. Chem. 61±, 323 ( 1 9 5 2 ) . 5". E. G. ROCHOW. . An i n t r o d u c t i o n to the chemistry of s i l i c o n e s . 2nd ed. John Wiley and Sons, Inc., New York. 1951. 6 . L. KAPLAN, W. L. KESTER and J . J . KATZ. J . Am. Chem. Soc. 7jj., 5531 ( 1 9 5 2 ) . 7. J . M. HAMILTON, J r . Advances i n f l u o r i n e chemistry. V o l . 3 . E d i t e d by M. Stacey, J . C. Tatlow and A. G. Sharpe. But-terworths, London. 1963- PP• 1 1 7 - l 8 l . 8. L. HALUSKA. U. S. patent 2 , 8 0 0 , 4 9 4 ( 1 9 5 7 ) ; CA £l, 17982 ( 1 9 5 7 ) . 9 . R. N. HASZELDINE and J..C. YOUNG. J . Chem. Soc. 4503 ( I 9 6 0 ) . 10. A. M. GEYER and R. N. HASZELDINE. J . jChem. Soc. IO38 (19.57). 11. C. G. KRESPAN and V. A. ENGELHARDT. J . Org. Chem. 2 3 , 1565 ( 1 9 5 8 ) . 12. H. C. CLARK, S. FURNIVAL and J . T. KWON. Can. J . Chem. k l , 2889 ( 1 9 6 3 ) . 13. P. M. TREICHEL and F. G. A. STONE. Advances i n organometal-l i c c h emistry. V o l . 1. Edi ted by F. G. A. Stone and R. West. Academic Press, Inc., New York. 1964. pp. 11+3-217-14. "H. P. BRAENDLIN and E. T. McBEE. Advances i n f l u o r i n e chem-i s t r y . V o l . 3 . Edi ted toy M. Stacey, J.'C. Tatlow and A. G. Sharpe. Butterworths, London. 1963. pp. 1.-18. 15. J . R. LAGHER, J . J . McKINLEY, C. M. SNOW, L. MICHEL. G. NELSON and J . D. PARK. J . Am. Chem. Soc. JJ., 1330 ( 1 9 4 9 ) . 16. J . B. WILFORD and F. G. A. STONE. Inorg.'. Chem. k_, 93 ( 1 9 6 5 ) . 17. N. FUKUHARA and L. A. BIGELOW. J . Am. Chem. Soc. 6 3 , 788 (1941) 18. A. L. HENNE, J . W. SHEPARD and E. J . YOUNG. J . Am. Chem. Soc. 7 2 , 3577' ( 1 9 5 0 ) . 19. M. HAUPTSCHEIN and R. A. BRAUN. J . Am. Chem. Soc. 7 7 , 4930 ( 1 9 5 5 ) . ~ 2 0 . D. C. ENGLAND. J . Am. Chem. Soc. _8_3_, 2205 ( 1 9 6 1 ) . 2 1 . W. J . MIDDLETON and R. V. LINDSEY, J r . J . Am. Chem. Soc. 8 6 , 4948 ( 1 9 6 4 ) . ~ 116 2 2 . S. ANDREADES and D..C. ENGLAND. J . Am. Chem. Soc. 8 3 , k670 ( 1 9 6 1 ) . 2 3 . F. W. HOOVER, H. B. STEVENSON and H. S. ROTHROCK. J . Org. Chem. 2 8 , 1825 ( 1 9 6 3 ) . 2 k . I. L. KNUNYANTS, N. P. GANBARYAN, CH'ING-YEN CH'EN and E. M. ROKHLIN. Izv. Akad.' Nauk SSSR, Otd. Khim. Nauk 68k ( 1 9 6 2 ) . 2 5 . H. E. SIMMONS and D. W. WILEY. J . Am. Chem. Soc. 8 2 , 2288 ( I 9 6 0 ) . 2 6 . W. R. NES and A. BURGER. J . Am. Chem. Soc. 7_2, 5U09 ( 1 9 5 0 ) . 2 7 . P..E. NEWALLIS and E. J . RUMANOWSKI. J . Org. Chem. 2 9 , 31 Ik ( 1 9 6 k ) . 2 8 . D. W. WILEY and H. E. SIMMONS. J . Org. Chem. 29', 1876 ( 1 9 6 k ) . 2 9 . G. W. PARSHALL. Inorg. Chem. jj., $2 ( 1 9 6 5 ) . 3 0 . W. L. JOLLY and J . E. DRAKE. Inorganic s y n t h e s i s . V o l . V I I . E d i t e d by J . Kleinber.g* McGraw-Hill, New York. 1963. pp. 3k~m-3 1 . V. AUGER. Compt. rend. ik_2, 1152 ( 1 9 0 6 ) . 3 2 . A. E. GODDARD. " D e r i v a t i v e s of A r s e n i c " . In Textbook of i n -organic chemistry. V o l . X|{ Part I I . E d i t e d by J . N. F r i e n d . C. G r i f f i n and Co., Londol. 1930. p. ^ 2~. 33- W. STEINKOPF and W. MIEG. Ber. £3B, 1013 ( 1 9 2 0 ) . 3 k . W. M. DEHN and B. B. WILCOX. Amer. Chem. J . 3_£, 1 ( 1906) . 3 5 . F. F. BLICKE, L. D. POWERS and G. L. WEBSTER. J . Am. Chem., Soc. 5 k , 29U5 ( 1 9 3 2 ) . 3 6 . W. M. DEHN. Amer. Chem. J . 33_, 101 ( 1 9 0 5 ) . 3 7 . W. M. DEHN and F. WILLIAMS. Amer. Chem. J . k_0, 107 ( 1908) . 3 8 . W. M. DEHN. Amer. Chem. J . kjD, 120 ( 1908) . 3 9 . C R. McCOY and A. L. ALLRED. J . Inorg. N u c l . Chem. 2 5 , 1219 ( 1 9 6 3 ) . ~ ~ k 0 . R. K. HARRIS and R. G. HAYTER. Can. J . Chem. ]\2, 2285 ( 1 9 6 k ) . k l . W. R. CULLEN and N. K. HOTA. Can. J . Chem. i+_2, 1123 ( 1 9 6 k ) . k 2 . E. R. LIPPINGOTT and M. C. TOBIN., J . Am. Chem. Soc. 7 5 , k l k l ( 1 9 5 3 ) . ~ " k 3 . M^. P. BROWN and G. W. A.FOWLES. J . Chem. Soc. 2 8 l l ( 1 9 5 8 ) . kk. J . E. GRIFFITHS. Inorg. Chem. 2 , 375 ( 1 9 6 3 ) . 117. -45- C . R . D I L L A R D , E . H . M c N E I L L , D . E . .SIMMONS a n d J . B . Y E L D E L L . J . A m . C h e m . S o c . 80, 3607 ( 1 9 5 8 ) . 46. R . N . H A S Z E L D I N E . J . C h e m . S o c . 1748 ( 1 9 5 3 ) . 4 7 . R . ADAMS a n d C . S . P A L M E R . J . A m . C h e m . S o c . 1+2, 2375 ( 1 9 2 0 ) . 4®. R . ADAMS a n d C . S . P A L M E R . J . A m . C h e m . S o c . k]j., 1356 ( 1 9 2 2 ) . 49. W . R . C U L L E N a n d D . . C . F R O S T . C a n . J . C h e m . LLO , 390 ( 1 9 6 2 ) . 5 0 . D..S. P A Y N E . Q u a r t . R e v . _l£, 173 ( 1 9 6 1 ) . 5.1. H . G1LMAN a n d D . W I T T E N B E R G . J . O r g . C h e m . 2J_, 501 ( 1 9 5 8 ) . 5 2 . Ri G A L A S a n d N . D U F F A U T . C o m p t . r e n d . 2 l j £ , 906 ( 1 9 5 7 ) . 53« H . G , K ' J I V I L A . A d v a n c e s i n o r g a n o m e t a 11 i c c h e m i s t r y . V o l , 1. E d i t e d by F . G . A . S t o n e a n d R . W e s t . A c a d e m i c P r e s s , I n c . , New Y o r k . 1964- PP ' . 6 6 - 7 0 . 54- R . B A K E R , R . W. B O T T , C . EABORN a n d P . W. J O N E S . J . O r g a n o -m e t a l . C h e m . ±, 37 ( 1 9 6 3 ) . 55- . C . EABORN a n d O. W. STEWARD. P r o c . . C h e m . S o c . 59 ( 1963)"'. 5 6 . A . G . BROOK a n d W. W. L I M B E R G . - J ' . A m . C h e m . S o c . 8£, 832 ( 1963) 57- J • R . C H I P P E N F I E L D a n d R . H-. ; P R I N C E . . J . . C h e m . S o c . 3567 (1963)'. 5 8 . R . W. B O T T , C , EABORN a n d T . W. SWADDLE. J . C h e m . S o c . 2342 (1963) . 59- O . H . JOHNSON a n d E . A . S C H M A L L . J . A m . C h e m . S o c . 80, 2931 (1958) . — 60. R . E . D E S S E Y , T K I E B E R a n d F . P A U L I K . J . A m . C h e m . S o c . 86, 28 (1964) . ' _ 6 1 . D . C O O K . C a n . J . C h e m . 522 ( I 9 6 3 ) . 6 2 . M . F . L A P P E R T . J . C h e m . S o c . 8 l 8 ( 1 9 6 1 ) . 6 3 . P . N . GATES a n d E . E . MOONEY. J . C h e m . S o c . 4648' ( 196I+) . 64. J . K O V A C I C , K . POWELL a n d R . N . C H A D H A . A b s ' t r . . 149 t h A m e r . C h e m . S o c . M e e t i n g , D e t r o i t . 1965-6 5 . NT. J . J A N S S E N , H . G . A . . L U I J T E N a n d G . J . M . v a n d e r K E R K . J . O r g a n o m e t a l . C h e m . _1, 286 ( 1964) . 66. I . R.. B E A T I E , G . P . M c Q U I L L A N a n d R . H U L M E . C h e m . I n d . ( L o n d o n ) 1429 ( 1 9 6 2 ) . 67. H . C . C L A R K , R . J . O ' B R I E N a n d J . T R O T T E R . J . C h e m . S o c . 2332 (1964) . „ 68 . H . C . C L A R K a n d R . J . O ' B R I E N . I n o r g . C h e m . 2, 740 ( 1 9 6 3 ) . 118 69. A . N . P U D O V I K , A . A . MURATOVA a n d E . P . S E M K I N A . J . C h e m . U . S . . S . R . ( E n g . T r a n s l . ) 33, 3276 ( 1963) . G e n . 70. C . L . F R Y E . J . A m . C h e m . S o c . 86, 317© ( 19'6k) . 71. J . L . COREY a n d R . W E S T . J . A m . . C h e m . S o c . 8^, k03k ( 1963.) • 72. E.. R . . C L A R K . J . I n o r g . Nuc-1. .Chem. 2£, 353 '( 1.963).. 73. E . R , C L A R K . J . I n o r g . . N u c . l . C h e m . 2k., 8l (1962). 74- T . DROZDOVA, R . P . KRAVTSOVA a n d K. I . T O B E L K O . I z v . A k a d i N a u k S S S R , O t d . K h i m . N a u k .38 (1962). 7 5 . T . T A N A K A , M . KOMURA. Y . . KAWASAKI a n d R . OKAWARA. J . O r g a n o -' m e t a l . : C h e m . j . , 484 (196k). 76. L . R O N C U C C I, G. F A R A G L I A a n d R . B A R B I E R I . J . O r g a n o m e t a l . C h e m . J , , k27 ( 196k) . 77- R . OKAWARA a n d M.. WADA. J . O r g a n o m e t a l . C h e m . _1, 8l ( 1963) . 78. A . G . D A V I E S a n d W. R . S Y M E S . C h e m . C o m m u n . ' 25 (1965). 79. C . A , K R A U S E a n d W. N . G R E E R . J . A m . . C h e m . S o c . h£_, 3078 (1923). 80". J . D . P A R K , L . H . WILSON a n d J . R . L A C H E R . J . O r g . C h e m . 28, 1008 ( 1963) . 81. Y . K I T A H A R A , M . C . C A S E R I O , F . S C A R D I G L I A and. J . . D . R O B E R T S . J . A m . C h e m . S o c . 82, 3106 ( i960). 82. E . F . S I L V E R S M I T H a n d J . . D . R O B E R T S . J . A m . C h e m . S o c . 80, k083 (1958). ~ 83. S . D I X O N . J . O r g . C h e m . 21, k O O (1956). 8k. J . D . P A R K a n d R . F O N T A N E L L I . J . O r g . C h e m . 28, 258 ( 1963) . 85. R . . S U L L I V A N , J . R . L A C H E R a n d J . D . P A R K . J . O r g . C h e m . 29, 366k (196k). — 86. J . . D . . P A R K , M . L . . S H A R R A H a n d J . R . L A C H E R . J . A m . C h e m . S o c . 7_i, 2337 ( 19k9) . \ 87. J . T=. B A R R , K.. E . R A P P , R . ' L . P R U E T T , C . T . B A H N E R , J . D . G I B -SON a n d R . H . L A F F E R T Y , J r . J . A m . C h e m . S o c . 72, kk80 (1950). ~~ 88. R . F . S T O C K E L , M . T . B E A C H E N a n d F . H . - M E G S O N . C a n . J . C h e m . LL2, 2880 ( 196k) . 89. J . D . P A R K . C . M . SNOW a n d J . R . L A C H E R . J . A m . C h e m . S o c . 73, 2 3 4 2 . ( 1 9 5 1 ) • 90. J . . D . P A R K , J . R . D I C K a n d J . - R . L A C H E R . J . O r g . C h e m . 28, 1154 (1963). ' 119 •91. E". F . J E N N Y and J'.. D R U E Y . J . Am. Chem. Soc. 8 2 , 3 1 H (I960). 9 2 . . K . ' E . R A P P , P . L . P R U E T T , J . : T . B A R R , C . T . B A H N E R , . J . D . G I B -S O N and R . H . L A F F E R T Y , J r . J . Am. Chem.. Soc. 7 2 , 36k2 ( 1 9 5 0 ) . 9 3 - A . F E R R E T Y I and G . T E S I . Chem. Ind. (London) 1987 ( 1 9 6 k ) . 9 k . ' R . L . P R U E T T , J . T . B A R R , K . E . R A P P , C . T . B A H N E R , J . D . G I B -S O N and R . H . L A F F E R T Y , J r . J . Am. Chem. Soc. 72, 36I+6 ( 1 9 5 0 ) . 9 5 . T.. M I L L , J . 0 . R O D I N , R . M . S I L V E R S T E I N and C . W O O L F . J . Org. Chem. 2 8 , 836 ( 1 9 6 3 ) • 9 6 . C . 0 . P A R K E R . J . Am. Chem. Soc. 8 l , 2183 ( 1 9 5 9 ) . 97- I . L . K N U N Y A N T S , V . V . T Y U L E N E V A , E . Y . P E R O V A and R . N . S T E R -L I N . I . z v . Akad. Nauk S S S R , Ser. Khim. 10, 1797 ( 1 9 6 k ) . 98. W.. R . C U L L E N , D . S . D A W S O N , P . S . D H A L I W A L and G . E . S T Y A N . Chem. Ind. (London) 5 0 2 (1961+). 9 9 . R . N . H A S Z E L D I N E . J . Chem. Soc. 3559 ( 1 9 5 3 ) . 100. W . R . C U L L E N and P . S . D H A L I W A L . Unpublished r e s u l t s . 101. W . T . M I L L E R , J r . , E . W . F A G E R and P . H. . G R I S W O L D . J . Am. Chem. S o c , 7 2 , 36k2 ( 1950) . 102. M . D.. H U R W I T Z and W . T . M I L L E R . 1^ A b s t r a c t of pap-ers. 1 lk£it Meeting, Amer. Chem. S o c , Washington, D , C . August 19k0. p. k - L . 103. M.. W . B U X T O N and J . C . T A T L O W . J . Chem. S o c 1177 ( 1 9 5 k ) . 10k. I . . L . . K N U N Y A N T S , M . P . K R A S U S K A Y A , E . I . M Y S O V and I . A . M U K H -T A R O V . Izv. Akad. Nauk S S S R , Otd. Khim. Nauk 2 l k l ( 1 9 6 2 ) . 105. M . T A K A H A S K I , D . R . D A V I S and J . D . R O B E R T S . J . Am. Chem. Sec. 8k_, 2935 ( 1962) . 106. w.. D. PHILLIPS.. J . Chem. Phys. 2 5 , 9k9 ( 1 9 5 6 ) . 1 0 7 . J . N. SHOOLERY. D i s c u s s i o n s Faraday Soc. 29, 215 ( 1 9 5 5 ) -108. R. J . ABRAHAM and L. CAVALLI. :Mol. Phys. In p r e s s . 109. L.. D. HALL and J . MANVILLE. Unpublished. r e s u l t s . 110. M. . KARPLUS. J . Am. Chem.. S o c 8£, 2 8 7 O ( 1 9 6 3 ) . 111. H. C. CLARK, J . T. KWON, L. W. REEVES and J . Chem. k_l, 3005 (1963) . E. J . WELLS. Can. 112. E . . SWARTS. J . Chem. Phys. J 7 , 3 ( 1 9 1 9 ) . 120 113- D. S E Y F E R T H . P r o g r e s s i n i n o r g a n i c c h e m i s t r y . V o l . 3> E d i t e d by F . A l b e r t C o t t o n . I n t e r s c i e n c e P u b . , J o h n W i l e y a n d S o n s , New Y o r k . 1962. p p . 188-207-i l k . L. H. SOMMER, D . L . B A I L E Y , G . M . G O L D B E R G , C. E . B U C K , T . S . B Y E , F . J . EVANS a n d F . C . WHITMORE. J . A m . C h e m . S o c . 7 6 , 1613 ( 195k) . 115. D. T. H U R D . J . A m . C h e m . S o c . 67, 1813 (191+5). 116. C. L . A G R E a n d W. H I L L I N G , J . A m . C h e m . S o c . 7J1, 3895 (1952). 117. V . F . MIRONOV, N . G . D Z H U R I N S K A Y A a n d A . D. P E T R O V . D o k l . A k a d . N a u k SSSR 131, 98 ( i 9 6 0 ) . 118. V . F . MIRONOV, Y." P. EGOROV a n d A . D. P E T R O V . I z v . A k a d . N a u k S S S R , O t d . K h i m . N a u k li+00 (1959). 119. A . L . HENNE a n d W. G . F I N N E G A N . J . A m . C h e m . S o c . 7_1, 298 (191+9). 120. R . N . H A S Z E L D I N E . . N a t u r e 165, 152 (1950). 121 W. G . F I N N E G A N a n d W. P. N O R R I S . J . O r g . C h e m . 2 8 , 1139 (1963). 122. R- N . H A S Z E L D I N E . J . C h e m . S o c . 3I+9O (1952). 123. W. C H A N E Y , U . S . p a t e n t 2,522, 566 (1950); C A k5, 2015 (1951). 12k. c . G . K R E S P A N , B . C . M c K U S I C K a n d T . L . C A I R N S . J . A m . C h e m . S o c . 8 2 , 1515 (I960) . 125. F . W. STACEY and J . F . H A R R I S , J r . J . A m . C h e m . S o c . 8 5 , 963 (1963). "~ 126. W. R . C U L L E N and D . S . DAWSON. U n p u b l i s h e d r e s u l t s . 127 . W. R . C U L L E N , D . S . DAWSON a n d G . E . S T Y A N . J . O r g a n o m e t a l . C h e m . I n p r e s s . 128. J . L . B O S T O N , S . O. G R I M a n d G . W I L K I N S O N , J . C h e m . S o c . 3I+68 (1963). 129 . ' J < L . B O S T O N , D . W. A . SHARP a n d G . W I L K I N S O N . J . C h e m . S o c . 3k88 (1962). 130. P . M . T R E I C H E L , E . P I T C H E R a n d F . G . A . S T O N E . I n o r g , C h e m . J . , 511 ( 1962) . 131. c . A . KRAUS a n d W. N . G R E E R . J . A m . C h e m . S o c . kj±, ' 2629 (1922). 132.. w. P . N E U M A N N . A n g e w . C h e m . I n t e r n . E d . E n g l . 2, 165 ( 1963) . 133. c . A . KRAUS a n d E . A . F L O O D . J . A m . C h e m . S o c . 5k_, 1635 (1932). 13U. J . M . S H A C K E L F O R D , H . de S C H M E R T Z I N G , C . H . HEUTHER a n d H . P O D A L L . J . O r g . C h e m . 2 8 , 1700 (1 9 6 3 ) . 121 135- T . M O E L L E R a n d D . C . EDWARDS. I n o r g a n i c s y n t h e s i s . V o l . I V . E d i t e d by J . C . B a i l a r , J r . M c G r a w - H i l l , New Y o r k . 1953-p . 119. 1 3 6 . ' J . G . A . L U I J T E N a n d G . J . M . v a n d e r K E R K . I n v e s t i g a t i o n s " ^ t h e f i e l d o f o r g a n o t i n c h e m i s t r y . T i n R e s e a r c h I n s t i t u t e , G r e e n f o r d , M i d d l e s e x , E n g l a n d . 1955. 137.. H , C . C L A R K a n d C . J . W I L L I S . J . A m . C h e m . S o c . 8 2 , 1888 ( i 9 6 0 ) . 138. L . J . B E L L A M Y . The i n f r a r e d s p e c t r a o f c o m p l e x m o l e c u l e s . 2nd e d . J o h n W i l e y a n d S o n s , I n c . , New Y o r k . 1958. 139. E . EBSWORTH. V o l a t i l e s i l i c o n c o m p o u n d s . P e r g a m o h P r e s s , New Y o r k . 1963. p p . 8 - 9 . I k O . R. F . F U L T O N . P h . D . T h e s i s , P u r d u e U n i v e r s i t y . I 9 6 0 . l k l . D . S E Y F E R T H a n d L . G . V A U G H A N . J . O r g a n o m e t a l . C h e m . 1, 138 , ( 1 9 6 3 ) . • • " ~ l k 2 . S . I . M I L L E R . J . Am. C h e m . S o c . 7 8 , 6091 ( 1 9 5 6 ) . I U 3 J . . L . B U R N E L L E . T e t r a h e d r o n 2 0 , 2k03 ( 1 9 6 k ) . l k k . R . A . B E N K E S S E R , M . L . BURROWS, L . E . N E L S O N a n d J . V . S W I S H E R . J . A m . C h e m . S o c . 8^, k385 ( 1 9 6 1 ) . I k 5 . W. R . C U L L E N , P.. S . DHALIWAL a n d W. B . FOX". . I n o r g . C h e m . 3 , 1332 ( 1 9 6 k ) . 

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