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Some reactions of alkyl iodides and perfluoroalkyl iodides with iodides of group V elements Baig, Mirza Mohammed 1961

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SOME REACTIONS OF ALKYL IODIDES AND PERFLUOROALKYL IODIDES /  WITH IODIDES'OF GROUP V ELEMENTS by MIRZA MOHAMMED BAIG M . S c , U n i v e r s i t y o f K a r a c h i , 1952  A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE i n t h e Department o f CHEMISTRY  We accept t h i s t h e s i s as conforming r e q u i r e d standard  to the  THE UNIVERSITY OF BRITISH COLUMBIA October,  1961  In p r e s e n t i n g the  this thesis i n p a r t i a l fulfilment of  requirements f o r an advanced degree a t the  British  Columbia, I agree t h a t the  a v a i l a b l e f o r reference  and  study.  University  of  L i b r a r y s h a l l make i t f r e e l y I f u r t h e r agree t h a t  permission  f o r e x t e n s i v e copying o f t h i s t h e s i s f o r s c h o l a r l y purposes may g r a n t e d by  the  Head o f my  It i s understood t h a t f i n a n c i a l gain  Department o f  representatives.  c o p y i n g or p u b l i c a t i o n o f t h i s t h e s i s f o r  s h a l l not  be  a l l o w e d w i t h o u t my  Q^Kfi/w^i  The U n i v e r s i t y o f B r i t i s h Vancouver 8, Canada. Date  Department o r by h i s  be  Columbia,  written  permission.  ii  ABSTRACT  The r e a c t i o n o f a l k y l i o d i d e s w i t h p h e n y l - i o d o - a r s i n e s i n the presence  o f mercury has been found t o y i e l d arsonium d e r i -  v a t i v e s o f t r i i o d o m e r c u r y ( I I ) . E x t e n s i o n o f these r e a c t i o n s t o other i o d i d e s o f the Group V elements showed t h a t when r e a c t e d w i t h iodomethane and mercury, phosphorus t r i i o d i d e gave t h e 1:1 complex o f t r i m e t h y l p h o s p h i n e and m e r c u r i c i o d i d e ; antimony t r i i o d i d e gave t e t r a m e t h y l s t i b o n i u m t r i i o d o m e r c u r y ( I I ) ; diiodophenylstibine reacted only to a l i m i t e d bismuth t r i i o d i d e gave an u n s t a b l e p r o d u c t .  extent; and Trifluoroiodo-  methane f a i l e d t o r e a c t w i t h the Group V i o d i d e s i n t h e presence of mercury. mercuric  Because o f the p o s s i b i l i t y t h a t 1:1 t e r t i a r y a r s i n e  i o d i d e complexes a r e i n t e r m e d i a t e s i n the r e a c t i o n s  which g i v e r i s e t o arsonium t r i i o d o m e r c u r y ( I I ) d e r i v a t i v e s , the r e a c t i o n o f these complexes w i t h a l k y l i o d i d e s was i n v e s t i g a t e d . In a l l cases i n v e s t i g a t e d u s i n g iodomethane, d i r e c t r e a c t i o n o c c u r r e d w i t h t h e formation o f arsonium t r i i o d o m e r c u r y ( I I ) derivatives.  Iodoethane, bromoethane and t r i f l u o r o i o d o m e t h a n e  were found t o r e a c t only t o a s l i g h t e x t e n t , i f a t a l l , w i t h t e r t i a r y a r s i n e mercuric  i o d i d e complexes.  • • »  XXX  TABLE OF  CONTENTS  Page I. II. III.  Introduction  1  D i s c u s s i o n and R e s u l t s  3  Experimental  17  S e c t i o n A - Reactions o f Iodo-Arsines w i t h A l k y l I o d i d e s i n the Presence o f Mercury  18  S e c t i o n B - Reactions of Other I o d i d e s o f the Group V Elements w i t h Iodomethane and T r i f l u o r o i o d o m e t h a n e i n the Presence of Mercury  23  S e c t i o n C - R e a c t i o n s of T e r t i a r y A r s i n e Complexes w i t h Iodomethane, T r i f l u o r o i o d o m e t h a n e and Iodoethane  28  S e c t i o n D - R e a c t i o n of P h e n y l d i m e t h y l a r s i n e w i t h Trifluoroiodomethane  36  T a b l e - R e a c t i o n s of Iodo-Arsines and Analogues o f Group V  38  T a b l e - R e a c t i o n s o f T e r t i a r y A r s i n e Complexes  39  Bibliography  40  iv  ACKNOWLEDGEMENT  I am deeply g r a t e f u l t o Dr. W. R. C u l l e n f o r h i s  constant  guidance and a s s i s t a n c e throughout the complete experimental work and a l s o f o r t h e o r e t i c a l d i s c u s s i o n s .  I a l s o w i s h t o thank  Dr. N. B a r t l e t , Dr. C. W i l l i s and Dr. A. A. Beg, f o r t h e i r a s s i s t a n c e on s e v e r a l o c c a s i o n s , for  t h e i r cooperation.  and other members o f t h e s t a f f  My thanks a r e a l s o due t o Mrs.  who has been v e r y h e l p f u l i n connection  M.  Zell,  with infrared analysis.  L a s t l y I wish t o express my g r a t i t u d e and s i n c e r e thanks t o Dr. C. A. McDowell f o r t h e f a c i l i t i e s , for  t o Colombo P l a n and N.R.C.  t h e f i n a n c i a l a s s i s t a n c e , and t o S. M. C o l l e g e f o r  leave t o a v a i l t h i s  opportunity.  granting  1  INTRODUCTION  R e c e n t l y some new  methods o f p r e p a r i n g a l k y l or a r y l ,  t r i f l u o r o m e t h y l a r s i n e s have been d e s c r i b e d (1) ( 2 ) . c u l a r i n t e r e s t i s one  R A s I 4- Hg + I C F 2  2  parti-  i n which i o d o - a r s i n e s are r e a c t e d w i t h  t r i f l u o r o i o d o m e t h a n e i n the presence  R Asl  Of  o f excess mercury.  =  R As»CF  3  =  R As(CF >  R  =  CH  3  + 2Hg + 2 I C F  2  + Hgl  3  3  3  2  or C H 6  2  + 2HgI  2  5  The method i s remarkable f o r i t s s i m p l i c i t y .  The r e a c t i o n s  occur a t room temperature i n good y i e l d , and o f f e r a much more convenient  r o u t e to s u b s t i t u t e d t r i f l u o r o m e t h y l a r s i n e s than  e a r l i e r exchange r e a c t i o n methods (3) 2(CH ) As + CF I 3  3  (CF ) As 3  3  3  + CH I 3  (4).  =  (CH ) As CF  =  (CF ) As  3  3  2  2  the  CH  3  3  +  (CH ) AsI 3  4  + CF I 3  P r e l i m i n a r y i n v e s t i g a t i o n a l s o showed t h a t when iodomethane was  used i n s t e a d of t r i f l u o r o i o d o m e t h a n e i n s i m i l a r r e a c t i o n s ,  the products were o f the type p r e v i o u s l y formulated as arsonium d e r i v a t i v e s of t r i i o d o m e r c u r y ( I I ) . Thus t r i i o d o m e r c u r y ( I I ) was  tetramethylarsonium  produced i n good y i e l d from the r e a c t i o n  o f iodomethane and excess mercury w i t h the compounds i o d o d i m e t h y l a r s i n e , d i i o d o m e t h y l a r s i n e and a r s e n i c t r i i o d i d e ( 5 ) . The p r e s e n t work i s a c o n t i n u a t i o n o f these The  investigations.  f i e l d o f study has been e n l a r g e d to i n c l u d e other analogous  2 alkyl  iodide reactions  tives  of other  m a i n l y on  and  to extend the  e l e m e n t s i n Group V.  s e e i n g what r e a c t i o n s w i l l  studies  to  A t t e n t i o n has o c c u r , and  new  effort  products  has  b e e n made t o  formed except o n l y  characterisation.  Infra-red  and  the The  to d e r i v e  to  to a s s i s t X-ray  of  the  their  powder  i n a comparative sense w i t h o u t  d e t a i l e d i n t e r p r e t a t i o n s from the  spectra  photographs. reactions  of a l k y l  complexes c o n t a i n i n g because of  the  intermediates tives  incidentally  focussed  reactions.  properties  s p e c t r o s c o p y and  photography have been u s e d o n l y attempting  study the  been  deriva-  i f possible  e l u c i d a t e a p o s s i b l e c o u r s e o r mechanism o f t h e s e H e n c e , no  iodo  mercuric  possibility i n the  iodides with t e r t i a r y  of triiodomercury  i o d i d e have a l s o been  that  reactions (II).  arsine  similar  investigated  a r s i n e complexes  giving rise  to arsonium  are  deriva-  3  DISCUSSION AND  RESULTS  As d e s c r i b e d i n the I n t r o d u c t i o n , the  methyl-iodo-arsines  r e a c t w i t h iodomethane i n the presence o f mercury to g i v e tetramethylarsonium  triiodomercury  (II) (5).  I t has now  been  found t h a t p h e n y l - i o d o - a r s i n e s undergo s i m i l a r r e a c t i o n s .  Thus  i o d o d i p h e n y l a r s i n e when shaken w i t h mercury and iodomethane g i v e s dimethyldiphenylarsonium  triiodomercury ( I I ) .  Similarly  d i e t h y l d i p h e n y l a r s o n i u m t r i i o d o m e r c u r y ( I I ) i s o b t a i n e d when iodoethane i s used.  Diiodophenylarsine gives trimethylphenyl-  arsonium t r i i o d o m e r c u r y ( I I ) and t r i e t h y l p h e n y l a r s o n i u m t r i i o d o mercury ( I I ) under s i m i l a r c o n d i t i o n s . d e r i v a t i v e s are new melting points.  These phenyl-arsonium  compounds and are y e l l o w s o l i d s w i t h  They are e a s i l y s o l u b l e i n acetone and a l c o h o l .  T h e i r m o l e c u l a r weights i n camphor i n d i c a t e t h a t they monameric.  T h i s excludes  s t r u c t u r e and suggests  a 3 coordinate Hgl^ i o n .  H. J . C a v e l  c o n c l u s i o n s are based mainly  and  f o r the e x i s t e n c e of H g l ^  i o n i n compounds o f the type R^NHgl^ and R^SHgl^. on s o l u b i l i t y  Their  (polar),  c o n d u c t i v i t y and molecular weight determinations d i s s o c i a t i o n i n t o two  are  the p o s s i b i l i t y o f halogen b r i d g e d  S. Sugden (6) obtained some evidence  The  low  electrical  (indicate  ions).  i o d o - p h e n y l - a r s i n e s r e a c t more r e a d i l y - w i t h a l k y l  i o d i d e s than w i t h t r i f l u o r o i o d o m e t h a n e .  Iododiphenylarsine,  4 mercury and iodomethane give about 90% y i e l d (Table) of the arsonium derivative of triiodomercury (II) - the y i e l d from corresponding  iodoethane reaction i s about the same.  Under simi-  l a r conditions the reaction between iododiphenylarsine, mercury and trifluoroiodomethane gives a 76% y i e l d of the d i p h e n y l t r i fluoromethylarsine (2).  Similar reactions of the diiodophenyl-  arsine i n the presence of mercury give, with iodomethane, about 447o of the corresponding arsonium triiodomercury (II) complex, and with iodoethane about 337« of the arsonium triiodomercury (II) complex, but with trifluoroiodomethane only 107  o  fluoromethylarsine (2).  of p h e n y l b i s t r i -  Arsenic t r i i o d i d e , mercury and iodo-  methane give a 32% y i e l d of tetramethylarsonium (II) (7) but the analogous reaction with does not seem to occur (5).  triiodomercury  trifluoroiodomethane  In the case of the  iodo-phenyl-  arsines one observes a decreasing rate of reaction as the number of iodine atoms attached to the arsenic increase from one to three.  Both iodomethane and trifluoroiodomethane show t h i s  order of r e a c t i v i t y .  In some of these reactions a l k y l mercuric iodides are formed as byproducts. Rl + Hg  They probably r e s u l t from a side reaction  } RHgl which would be catalysed by any free iodine  present i n the iodo-arsines (8).  5 The study of reactions of this type was extended to other Group V iodides (Table).  subsequently In the case of phos-  phorus the reactions of phosphorus t r i i o d i d e with iodomethane and with trifluoroiodomethane i n the presence of mercury were investigated.  Like arsenic t r i i o d i d e (5) phosphorus t r i i o d i d e  does not react with trifluoroiodomethane i n the presence of mercury, but i t d i f f e r s from the arsenic t r i i o d i d e i n i t s reaction with iodomethane i n the presence of mercury. products are obtained from t h i s reaction.  Two  The main product i s a  yellowish white s o l i d , which could not be obtained pure even after repeated c r y s t a l l i s a t i o n from acetone and alcohol. melting point ranged between 165-170°.  The  The analysis of this  impure product roughly corresponded to the 1:1 adduct of trimethylphosphine and mercuric iodide.  The impure reaction  product was subsequently found to be i d e n t i c a l with the pure 1:1 adduct obtained d i r e c t l y from the reaction of trimethylphosphine and mercuric iodide. complex was 197-200°.  The melting point of the pure  The complex was very s l i g h t l y soluble i n  acetone or alcohol. The other product from t h i s reaction, formed i n a very small amount, was a yellow waxy substance.  I t was impure and melted  o between 85-100 .  The analysis corresponded to C5H^3PHgl2.4.  It  may or may not be impure tetramethylphosphonium triiodomercury (II). Antimony t r i i o d i d e closely resembles arsenic t r i i o d i d e i n  6  i t s reactions with iodomethane and trifluoroiodomethane i n the presence of mercury.  The iodomethane reaction gives tetramethyl-  stibonium triiodomercury (II) ( y i e l d 41%) which, l i k e the corresponding arsonium triiodomercury (II) complex, i s a yellow s o l i d o (m.p.167 ).  As expected trifluoroiodomethane, antimony t r i i o d i d e  and mercury do not give any trifluoromethy1-antimony  compounds.  The reaction of iodomethane with diiodophenylstibine i n the presence of mercury gives only a trace of yellow product. not i d e n t i f i e d but could probably be  This was  trimethylphenylstibonium  triiodomercury ( I I ) . I f t h i s i s so the y i e l d i s s i g n i f i c a n t l y /  low.  Diiodophenylstibine d i f f e r s from the corresponding arsine  in not reacting with trifluoroiodomethane.  From this i t would  appear that iodo-stibines are less reactive than iodo-arsines. However the evidence from the reaction of iodomethane with antimony t r i i o d i d e i n the presence of mercury does not concur with t h i s view.  The y i e l d of stibonium triiodomercury (II)  derivative from this reaction i s 41%.  The corresponding  reac-  tion of arsenic t r i i o d i d e (7) gives only 327 y i e l d of arsonium c  triiodomercury ( I I ) . However the present information i s not s u f f i c i e n t for making any generalisation. Unfortunately  the  reactions of iododiphenylstibine could not be studied as attempts to prepare this iodo-stibine i n a pure state were not successful. As expected bismuth t r i i o d i d e , trifluoroiodomethane mercury do not react.  The corresponding  and  iodomethane reaction  7 a l s o does not g i v e any  s o l i d bismuthomium complex o f t r i i o d o -  mercury ( I I ) . The acetone e x t r a c t o f the r e a c t i o n product yellow.  I t i s d i f f i c u l t to say whether i t c o n t a i n s  is  tetramethyl  bismuthomium t r i i o d o m e r c u r y ( I I ) i n s o l u t i o n or the y e l l o w c o l o u r i s j u s t due  to a s o l u t i o n of bismuth t r i i o d i d e i n  F u r t h e r work i s necessary  acetone.  to determine the p o s s i b i l i t y o f com-  p l e x formation i n s o l u t i o n .  At present  i t i s o n l y p o s s i b l e to  say t h a t the bismuthomium t r i i o d o m e r c u r y complex i s e i t h e r not formed o r , i f formed, i t i s u n s t a b l e i n the s o l i d s t a t e . In g e n e r a l one  can conclude  from these o b s e r v a t i o n s  that  the t r i i o d i d e s o f the Group V show no tendency t o r e a c t w i t h t r i f l u o r o i o d o m e t h a n e i n the presence o f mercury.  Their behavi-  our w i t h iodomethane i s somewhat i r r e g u l a r and no g e n e r a l i s a t i o n can be made. One  r e a c t i o n o f an i o d o - a r s i n e i s known i n which the p r o -  duct i s s i m i l a r to t h a t o b t a i n e d i n the r e a c t i o n o f phosphorus t r i i o d i d e , mercury and  iodomethane.  Thus  iododimethylarsine  r e a c t s w i t h iodoethane i n the presence o f mercury g i v i n g the 1:1  adduct o f d i m e t h y l e t h y l a r s i n e and m e r c u r i c  ever, the main products  iodide (7).  from most o f these r e a c t i o n s are  How-  either  onium type d e r i v a t i v e s of t r i i o d o m e r c u r y ( I I ) or t r i f l u o r o m e t h y l arsines ( 2 ) .  I t i s t h e r e f o r e suggested  t h a t the primary r e a c t i o n s  i n v o l v e the formation t e r t i a r y compounds R 3 M , i f t r i f l u o r o i o d o methane i s b e i n g used, or otherwise t e r t i a r y compounds w i t h m e r c u r i c  the 1:1  adducts o f the  i o d i d e s which when p o s s i b l e add  8 on more a l k y l h a l i d e t o g i v e onium d e r i v a t i v e s o f t r i i o d o m e r c u r y (II).  The non-formationnof m e r c u r i c  i o d i d e complex (R MR  *HgI )  2  2  i n t r i f l u o r o i o d o m e t h a n e r e a c t i o n s can w e l l be due t o 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 t r i f l u o r o m e t h y l group which c o n s i d e r a b l y reduces the donQr p r o p e r t y o f phosphorus o r a r s e n i c atom ( 9 ) . The  formation o f t h e s t a b l e 1 : 1 phosphine m e r c u r i c  i o d i d e com-  p l e x - i n t h e r e a c t i o n o f iodomethane w i t h phosphorus t r i i o d i d e i n the presence o f mercury - e s p e c i a l l y when a s i m i l a r s t a b l e complex i s n o t o b t a i n e d from t h e corresponding a r s e n i c t r i i o d i d e , may probably  reaction of  be connected w i t h t h e s t r o n g e r  donar p r o p e r t i e s o f phosphorus.  I t i s however d i f f i c u l t t o  understand why i o d o d i m e t h y l a r s i n e ,  iodoethane and mercury g i v e  the 1 : 1 complex but t h e c o r r e s p o n d i n g  r e a c t i o n of iododimethyl-  a r s i n e , iodomethane and mercury g i v e s t h e arsonium t r i i o d o mercury ( I I ) complex.  Two o f t h e more l i k e l y r e a c t i o n schemes  ( i l l u s t r a t e d f o r R2MI) a r e as f o l l o w s , (i)  R MI + Hg  > R MHgI  2  2  R'I——>  R MHgI + 2  R R'M 2  + Hgl  2  1 The  r e a c t i o n stops a t t h i s  stage i f R  the complex 1 : 1 R R M*HgI  i s formed.  2  R R*M 4- H g l 2  2  >R R'M'HgI 2  2  1 = CF^; i f R  = alkyl  2  though t h i s c o u l d be formed d i r e c t l y i n t h e second s t e p . 1 : 1 complex subsequently  adds R I t o g i v e onium d e r i v a t i v e o f  triiodomercury ( I I ) . R R'MHgI 2  2  The  + R'I  » R R2MHgI 2  3  (ii)  R MI + Hg  > R2MHgI  2  R MHgI + IMR 2  • > R M-MR + H g l  2  2  R M-MR 4- R ' l 2  The  2  2  > R R'M + R MI  2  2  2  subsequent steps a r e the same as i n ( i ) . The R MI which i s 2  regenerated i n t h i s mechanism forms R MHgI and continues t h e 2  cycle. The  preliminary  formation  o f the M-M bond i n t h e second  scheme i s not u n l i k e l y s i n c e i t has been found that when i o d o diphenylarsine  d i s s o l v e d i n benzene ( o r bromobenze o r ether)  and mercury a r e shaken together duct i s t e t r a p h e n y l d i a r s i n e when d i i o d o p h e n y l a r s i n e  a t o r d i n a r y temperature the p r o -  (CgH ) As-As(C^H^) 5  2  2  (10).  or diphenyldiiododiarsine  Similarly  (C5H5IAS-  AsICgHtj) d i s s o l v e d i n benzene i s shaken w i t h mercury the product i s arsenobenzene (11). C H AsI 6  5  2  + Hg 4- I A s C H 2  C H IAs-AsIC H 6  5  6  5  6  + Hg  > C H IAs-AsIC H + H g l  5  6  5  6  > C ^ A s = AsC H + 6  5  Hgl  5  2  2  Moreover, t h e As-As bond i s known t o be q u i t e l a b i l e t o t h e attack o f a l k y l iodides.  Cacodyl r e a d i l y r e a c t s w i t h excess o f  iodomethane forming tetramethylarsonium i o d i d e and t e t r a m e t h y l arsonium t r i i o d i d e .  I t has been suggested (12) t h a t t h e r e a c t i o n  involves the rupture  o f As-As bond and goes through t h e f o l l o w i n g  sequence. CH3I  (CH ) A s — A s (CH ) 3  2  3  2  J  ) (CH ) A s ~ - A s 3  2  (CH ) 3  2  10 (CH ) As + CHI  3 3  > (CH ) A s l  3  3 4  ( C H ) A s I + 2CH I 3  2  >  3  (CH ) AsI 3  4  3  S i m i l a r r e a c t i o n s occur when phenyl d e r i v a t i v e s c o n t a i n i n g As-As bonds r e a c t w i t h a l k y l i o d i d e s  (12).  The As-As bond i n  i s a l s o u n s t a b l e to t r i f l u o r o i o d o m e t h a n e t r i f luoromethylar s i n e and  cacodyl  at 20° g i v i n g d i m e t h y l -  iodobistrifluoromethylarsine  (1).  However the second r e a c t i o n scheme, although l i k e l y , cannot  be  used to e x p l a i n some s i m i l a r r e a c t i o n s of i o d o b i s t r i f l u o r o m e t h y l arsine  ( 5 ) , and  consequently the f i r s t  more r e a s o n a b l e e x p l a n a t i o n difficult the two  to d e v i s e  sequence, which o f f e r s a  o f these r e a c t i o n s , i s g i v e n .  experiments to show u n e q u i v o c a l l y  schemes ( i f e i t h e r ) i s i n o p e r a t i o n  P o s s i b l y both c o n t r i b u t e to a g r e a t e r  mental o b s e r v a t i o n  ( R A s ) H g l 2 r e a d i l y add 3  adduct i s p r o v i d e d  t h a t 2:1  2  i n a given  t h a t the  inter-  a r s i n e m e r c u r i c i o d i d e complexes  alkyliodide giving bis  p r e s e n t work, f u r t h e r c o n f i r m a t i o n r e a c t i n g iodomethane w i t h the 2:1 The  reaction.  by some e x p e r i -  (arsonium)  tetraiodomercury (II) d e r i v a t i v e s ( R ^ ' A s ^ H g l ^ (9).  mercuric i o d i d e .  which o f  or l e s s e r degree.  A d d i t i o n a l support for t h i s s u p p o s i t i o n mediate complex i s a 1:1  It is  o f t h i s has  In  the  been o b t a i n e d  complex o f t r i p h e n y l a r s i n e  and  product from t h i s r e a c t i o n i s a b i s  (arsonium) t e t r a i o d o m e r c u r y ( I I ) d e r i v a t i v e .  When t r i f l u o r o -  iodomethane or bromoethane i s used i n s t e a d of iodomethane, i s no r e a c t i o n .  by  Iodoethane under s i m i l a r c o n d i t i o n s  the product i s p r o b a b l y t r i p h e n y l e t h y l a r s o n i u m  there  reacts  triiodomercury  but (II).  11 A f a r more convincing proof of the proposed mechanism i s provided by the reactions of iodomethane with 1:1 adducts of various arsines and mercuric iodide.  The arsines studied for  t h i s reaction were diphenylmethylarsine, and t r i e t h y l a r s i n e . triiodomercury  phenyldimethylarsine  In a l l cases the corresponding arsonium  (II) derivative i s formed.  In the case of the  1:1  adduct of t r i e t h y l a r s i n e , the bis (arsonium) tetraiodomercury (II) derivative i s also formed. the 1:1  This may  be due to the tendency of  t r i e t h y l a r s i n e mercuric iodide adduct to disproportionate  i n solution and form the 2:3 arsine mercuric iodide complex (13). The conversion can be represented  as follows.  3 4-  2  Addition of iodomethane to the 1:1  complex should r e s u l t i n the  formation of an arsonium triiodomercury  (II) d e r i v a t i v e . How-  ever addition of the a l k y l iodide to the 2:3 adduct could give r i s e to both triiodomercury vatives.  (II) and tetraiodomercury (II) d e r i -  The eliminated arsine could also further react with  iodomethane and eliminated mercuric iodide giving further arsonium mercuri-iodides.  However the structure suggested  for the 2:3 adduct i s (C H ) As 2  5  3  As(C H )3 2  5  (13)  12 T h i s i s based o n l y on the c r i t e r i a n t h a t the molecule should have a c e n t r e o f symmetry. t a i n any  Because t h i s s t r u c t u r e does not  s i n g l e mercury atom bonded to two  not con-  a r s e n i c atoms i t seems  u n l i k e l y t h a t r e a c t i o n o f t h i s compound w i t h iodomethane would g i v e r i s e to arsonium tetraiodomercury  (II) d e r i v a t i v e s .  A  s t r u c t u r e which s t i l l f u l f i l s the s t r u c t u r a l c r i t e r i a n but which would g i v e tetraiodomercury  ( I I ) d e r i v a t i v e i s as f o l l o w s .  I t i s a l s o observed t h a t the corresponding iodoethane and the 1:1  r e a c t i o n between  adduct o f t r i e t h y l a r s i n e and  i o d i d e does not seem t o take p l a c e .  The  mercuric  l o s s o f iodoethane  d u r i n g t h i s experiment i s d i f f i c u l t to e x p l a i n , other than as l o s s d u r i n g h a n d l i n g , as an X-ray powder photograph o f the  product  a f t e r the r e a c t i o n , corresponds v e r y w e l l w i t h t h a t o f starting material. r e a c t i o n was  the  The m e l t i n g p o i n t of the complex a f t e r  the  c o n s i d e r a b l y lower than t h a t o f the pure substance  i n d i c a t i n g some s l i g h t r e a c t i o n not d e t e c t a b l e by the X-ray method had  taken p l a c e .  I t seems reasonable  t h i s l o w e r i n g o f the m e l t i n g p o i n t i s due o f the complex as d i s c u s s e d above.  to suggest t h a t  to d i s p r o p o r t i o n a t i o n  The n o n - r e a c t i o n  o f the com-  p l e x w i t h iodoethane i s i n harmony w i t h the f a c t t h a t when i o d o d i m e t h y l a r s i n e , iodoethane and mercury are r e a c t e d the r e a c t i o n goes o n l y as f a r as the formation o f the 1:1  adduct  13 (CH3)2 2% Sl2* c  H  This adduct does not add more iodoethane to give  the arsonium derivative of triiodomercury ( I I ) . There are some good reasons to believe that these reactions of a l k y l iodides with t e r t i a r y arsine adducts proceed by d i r e c t addition to the As-Hg bond rather than by d i s s o c i a t i o n of the As-Hg bond and subsequent formation of arsonium iodide which then reacts to give arsonium mercuric iodide complexes, R As .Hgl 3  R3AS  2  R As 4- C H 3 I  4-  Hgl  2  ) R3ASCH3I  3  R3ASCH3I 4- H g l  2  >R AsCH Hgl3 3  and s i m i l a r l y for the 2:1 adducts. following (1)  3  This follows from the  observations.  Triphenylarsine and iodomethane do not react at ordinary  temperature (14) showing that the addition of a l k y l iodide to the 2:1 adduct i s not l i k e l y to involve any scheme of reaction that requires a reaction of the type 4- CH3I ~ >  RM 3  (2)  R3MCH3I.  Complexes of the type R3As*Hgl2 appear to be associated i n  solution rather than dissociated and Mannnet a l . prefer a dimeric structure for these complexes both i n solution and s o l i d phase.  the  This structure involves iodine bridges and removes  the anomaly of tri-coordinate mercury. RoAs^  I  I  I  I  AsR  14 Coates and coworkers (9) regard c e r t a i n of these complexes as being present i n solution i n a monomer-dimer equilibrium.  In any  case i t i s easy to envisage d i r e c t addition of a l k y l iodide to these structures to give compounds of the type R^AsR'Hg^. (3)  Complexes of the type ( R ^ A s ^ H g ^ ^e a  s i m i l a r l y not  dissociated i n solution but i n t h i s case the compounds are monomeric, involving tetrahedral coordination round the mercury (13). Direct addition of a l k y l iodide to these compounds would thus be expected to give derivatives of the type (R^AsR ) 2^8*4• 1  Triphenyl arsine and trifluoroiodomethane high temperatures (2).  only react at  Therefore i t i s not surprising to f i n d  that no reaction occurs between trifluoroiodomethane  and the  2:1  o adduct of triphenylarsine and mercuric iodide at 20 .  The  f a i l u r e of bromoethane to react with the same 2:1 adduct could be due to the inherent i n s t a b i l i t y of any product containing such ligands as HgI Br2 or Hg^Br . 2  However the f a i l u r e of  the iodoethane to react with the 1:1 adduct of t r i e t h y l a r s i n e and mercuric iodide, e s p e c i a l l y when iodomethane reacts so r e a d i l y , i s d i f f i c u l t to understand.  Trifluoroiodomethane also  does not add to the 1:1 adduct of t r i e t h y l a r s i n e and mercuric iodide at 20°.  This difference i n behaviour from iodomethan^ —  could be due to reverse p o l a r i t y of the molecule CF3-I  4-  which  i f addition did occur could r e s u l t i n the formation of such species as R3ASI  associated with the species CF3Hgl2or CF3Hgl3.  Derivatives containing these mixed anions exist i n solution and  15 solids containing CJf^Hg^ ion have been i s o l a t e d (15) , however  + derivatives containing cations of the type R-jAsI  are unknown  apart from possibly compounds of the type R3ASI2 or R g A s l ^ H ) . Addition i n the same way containing R3ASCF3  as iodomethane would produce compounds  a group which i s known only for the case  R = CH3 (16). I t has been suggested (16) that exchange reactions between trimethylarsine and trifluoroiodomethane probably go through the intermediate formation of an arsonium iodide 2(CH ) As + C F I 3  3  > (CH ) AsCF  3  3  I 1  \  (CH )3As; 3  Intermediates  2  .CF3  3  +  t  (CH^AsI  ^1  of t h i s type can form only i f the lone p a i r of  electrons on arsenic atom i s a v a i l a b l e .  I t has been experimentally o  found (5) that t r i e t h y l a r s i n e and trifluoroiodomethane at  100  react as follows. 100° (C H ) As + CF I 2  5  3  3  > (C H ) AsCF 2  +  5  2  3  (70%)  (C H )4Asl 2  5  4- C H5As(CF3) 2  2  (trace)  giving 70% y i e l d of diethyltrifluoromethylarsine.  However the o  1:1 adduct (C Hcj) As. *HgI and trifluoroiodomethane at 100 2  3  2  only a trace of diethyltrifluoromethylarsine.  give  This c l e a r l y  shows that i n t h i s case the lone p a i r of electrons on arsenic i s already occupied by coordinate bonding to the mercury atom, and consequently  the intermediate of the type  16 .CF (C H ) AsC' ^1 2  i s not formed.  5  3  3  I t also follows that there i s l i t t l e d i s s o c i a -  t i o n of the As-Hg bond, since any t r i e t h y l a r s i n e formed by the breaking of t h i s bond could r e a d i l y react with t r i f l u o r o i o d o o methane at 100  to give diethyltrifluoromethyl arsine.  I t has been found that phenyldimethyl arsine and o iodomethane do not react even at 100  .  trifluoro-  The presence of the more  electronegative phenyl group seems to decrease the a v a i l a b i l i t y of the lone p a i r of electrons and thus prevents the formation of an intermediate  arsonium iodide complex as discussed above.  However at 170° reaction occurs giving many products containing CF  group including C H As(CF3) ; C H A s ( C F ) ; C H As.CF (CH );  3  6  5  2  3  C H .CF ; CF H; CH I, C ^ A s ( C H ) I . 6  5  3  3  3  3  3  3  that reaction occurs by r a d i c a l attack.  3  2  6  5  3  3  Thus i t i s very l i k e l y I t can also be suggested  that the s l i g h t reaction between trifluoroiodomethane  and  the  1:1 adduct of t r i e t h y l a r s i n e and mercuric iodide at 100° i s due to a r a d i c a l reaction.  17  EXPERIMENTAL Techniques: (a)  Vacuum System:-  A suitable (hard glass) vacuum system was  constructed f o r the handling of the v o l a t i l e materials i n the absence of a i r and moisture, and f o r trap-to-trap d i s t i l l a t i o n of v o l a t i l e mixtures at low pressures.  The system was also pro-  vided with a mercury d i f f u s i o n pump and a mercury manometer. (b)  Infrared:-  Infrared spectra were taken on a Perkin Elmer  Model 21 machine, equipped with sodium chloride optics. were examined as potassium bromide p e l l e t s .  Solids  L i q u i d samples were  run as thin films between sodium chloride discs, and f o r gaseous samples a suitable c e l l which could be evacuated and f i l l e d to the desired pressure by connecting to the vacuum system was used. (c)  X-ray:-  X-ray powder photographs  of s o l i d products were  taken with n i c k e l f i l t e r e d Cu k^; radiation at 40 k.v.  The X-ray  source and the powder camera of conventional design were supplied by General E l e c t r i c Company. was 45 cms. (d)  Shaker:-  The circumference of the camera  The films were usually exposed for 12 hours. Continuous shaking of reactants f o r long duration  was conveniently achieved by using a shaking machine with a horizontal action (Eberbach- Ann Arbor, Mich.). Unless otherwise mentioned a l l reactions were carried out i n sealed tubes i n the absence of a i r and l i g h t .  Since the mater-  i a l s generally handled were l i k e l y to produce harmful effects i f  18 i n h a l e d , v o l a t i l e m a t e r i a l s were manipulated  i n s i d e the vacuum  system; i n v o l a t i l e l i q u i d s and s o l i d s were handled i n an  efficient  fume hood. M i c r o a n a l y s e s of the products were made by Dr. A l f r e d Bernhardt  - M a x - p l a n c k - I n s t i t u t , Mulheim  (Ruhr).  SECTION A Reactions o f Iodo-Arsines w i t h A l k y l Iodides i n the Presence  o f M e t a l l i c Mercury uft'Hv  (i)  R e a c t i o n o f I o d o d i p h e n y l a r s i n e i» Iodomethane i n the  Presence  o f Mercury. I o d o d i p h e n y l a r s i n e was  prepared by the r e a c t i o n of fuming  h y d r o i o d i c a c i d on b i s ( d i p h e n y l a r s i n e ) oxide a t 1 0 0 ° oxide was  prepared from phenylmagnesium bromide and  oxide (18).  The  arsenious  was  c r y s t a l l i z e d from benzene and o f o o o b t a i n e d as a y e l l o w s o l i d m.p. 46 [ l i t . v a l u e 45 t o 46  (17)  J.  The  The  (17).  impure i o d i d e was  i o d i d e (10.2  g . ) , mercury (208  (60.7) were shaken a t 2 0 °  f o r 21  were e x t r a c t e d w i t h acetone.  days.  g.) and  The contents of the  From t h i s a y e l l o w product  l i s e d out, m e l t i n g i n the range 1 2 2 - 1 3 1 ° .  I t was  c u l t to o b t a i n a sharp m e l t i n g product even a f t e r crystallisations. melted a t 1 3 1 °  I t was  and was  iodomethane  found  tube  crystaldiffi-  repeated  a l s o noted t h a t most o f the product  p r o b a b l y accompanied by a s m a l l amount o f o  i m p u r i t y m e l t i n g a t 122 was  .  By c a r e f u l m a n i p u l a t i o n , the product  f i n a l l y separated i n t o two  fractions.  One  fraction  t a i n e d o n l y a t r a c e of t h i s probable i m p u r i t y m e l t i n g a t  con122°;  19 the other contained a somewhat larger amount of i t . The infrared spectra and X-ray powder photographs of both fractions were compared.  They appeared to be almost  identical.  The microanalysis of the purer f r a c t i o n (melting mostly at 131°) corresponded to diphenyldimethylarsonium triiodomercury ( I I ) . Anal:-  Found:  C, 19-9; Mol. wt.  Calculated for  H, 1-6;  Hg, 23'6;  I, 45*4%;  Hg, 23'9;  I, 45*3%;  814  (C H ) As(CH3) HgI : 6  5  2  C, 19'9; Mol. wt.  2  3  H, 1-9; 841  The y i e l d from t h i s reaction corresponded to 91%. In view of the d i f f i c u l t y of obtaining a sharply melting product, attempts were made to determine whether the impurity was methylmercury iodide or the .1:1 adduct of diphenylmethylarsine and mercuric iodide (preparation described below). Comparison of X-ray*powder photographs of these substances with that of the impure reaction product obtained above showed that there was iodide.  l i t t l e p r o b a b i l i t y of the impurity being methylmercury However nothing d e f i n i t e could be said about the pre-  sence or the absence of the 1:1 arsine complex. infrared spectra was Subsequently  Comparison of  inconclusive.  i t was observed that when diphenyldimethyl-  arsonium triiodomercury (II) was prepared through another route by reacting iodomethane and the 1:1 mercuric iodide complex of diphenylmethyl arsine, i t melted sharply at 122° when c r y s t a l l i s e d  20 from acetone.  When t h i s (pure) product was r e c r y s t a l l i s e d  alcohol the crystals showed a sharp m.p.  of 131°.  from  X-ray powder  photographs of diphenyldimethylarsonium triiodomercury (II) prepared above and of the same substance obtained from reaction of iodomethane and iododiphenylarsine i n the presence of excess mercury were i d e n t i c a l . (ii)  Reaction of Iododiphenylarsine with Iodoethane i n the Presence of Mercury. Iododiphenylarsine (10.0 g.), mercury (231.5 g.) and iodo-  ethane (60.1 g.) were sealed i n a tube and shaken continuously for 21 days.  On extraction with acetone and on  fractional  c r y s t a l l i s a t i o n two products, one colourless and the other yellow, were obtained.  In acetone, the colourless lamellar c r y s t a l l i n e  product was less soluble but i n alcohol i t was more soluble. The colourless product after repeated c r y s t a l l i s a t i o n from acetone melted at 187° and was i d e n t i f i e d as ethylmercury iodide. Anal:-  Found:  C, 6*83;  H, 1*41; Hg, 55*5;  Mol. wt. 340, m.p.  I, 35*7%;  187°  C^H^Hgl requires. C, 6-72;  H, 1»40; Hg, 56-3;  Mol. wt. 357, m.p.  I, 35*6%;  186° (8)  The y i e l d of the white product was 4 g. The yellow c r y s t a l l i n e product was repeatedly c r y s t a l l i s e d o from alcohol when i t melted at 86  and was i d e n t i f i e d as  diphenyldiethylarsonium triiodomercury ( I I ) .  Anal:-  Found:  C, 22*3;  H, 3'03;  Hg, 23'3;  I, 44-0%;  Hg, 23-2;  I, 43*8%;  Mol. wt. 918 Calculated f o r ^ ^ ^ A s ^ H ^ H g ] ^ : C, 22-1;  H, 2-30;  Mol. wt. 869 The y i e l d of t h i s product corresponded to y 90%. (iii)  Reaction of Diiodophenylarsine with Iodomethane i n the Presence of Mercury. Commercial diiodophenylarsine (10.3 g.), iodomethane  (51.2 g.) and mercury (119.0 g.), were sealed i n a tube and put on a shaker f o r 18 days.  On extraction with acetone and on  f r a c t i o n a l c r y s t a l l i s a t i o n two products were separated.  The  colourless product after repeated c r y s t a l l i s a t i o n melted at 147° and was i d e n t i f i e d as methylmercury  iodide ( y i e l d 37.6 g.).  Anal:-  Hg, 57*9;  Found:  C, 3*52;  H, 0*93;  I, 36' 8%; ,  Mol, wt. 319, m.p. 147° CH-jHgl requires: C, 3-50;  H, , 0*87;  Hg, 58-6;  I, 37*0%;  Mol. wt. 343, m.p. 152° (8) The yellow product was p u r i f i e d by c r y s t a l l i s a t i o n from alcohol. o I t melted at 128  and was i d e n t i f i e d as phenyltrimethylarsonium  triiodomercury (II) ( y i e l d 44%).  22 Anal:-  Found:  C, 12*9;  H, 1»8;  Hg, 24»4;  I, 48*0%;  Hg, 25-8;  I, 48*8%;  Mol. wt. 822 Calculated f o r C H As(CH ) HgT_ : 6  5  3  C, 13'7;  3  3  H, 1-8;  Mol. wt. 779 (iv)  Reaction of Diiodophenylarsine with Iodoethane i n the Presence of Mercury. Commercial diiodophenylarsine (10.0 g.), iodoethane  (64.3 g.) and mercury (203.2 g.) were s i m i l a r l y reacted for 18 days.  Extraction with acetone and f r a c t i o n a l  gave two products.  crystallisation  The colourless product, after repeated  c r y s t a l l i s a t i o n from acetone, melted between 182-184°.  If  o recrystallised  from alcohol i t melted at 187 .  corresponds to ethylmercury iodide. Anal:-  Found:  C, 6*61;  H, 1-17;  Result of analysis  The y i e l d was 12.6 g. Hg, 55*5;  I, 36*4%;  Mol. wt. 356, m.p. 187° C2H5HgI requires: C, 6'72;  H, 1*40;  Hg, 56-3;  I, 35*6%;  Mol. wt. 357, m.p. 186° (8) The yellow product after r e c r y s t a l l i s a t i o n  from alcohol  o melted at 129 . The a n a l y t i c a l arsonium triiodomercury ( I I ) .  data agree with p h e n y l t r i e t h y l The y i e l d was 6.6 g. or about 337 . 0  23 Anal:-  Found:  C, 17*8; Mol.  H, 2*44;  Hg, 24*1;  I, 46*7%;  Hg, 24*5;  I, 46*4;  wt. 847  Calculated f o r C H A s ( C H ) H g I : 6  5  2  C, 17*5; Mol.  5  3  3  H, 2*44;  wt. 821. SECTION B  Reactions of Other Iodides of the Group V Elements with Iodomethane and Trifluoroiodomethane in the Presence of Mercury (i)  Antimony T r i i o d i d e with Iodomethane i n the Presence of Mercury. Antimony t r i i o d i d e was prepared by reacting a suspension of  antimony powder with a solution of iodine i n benzene (19). Antimony t r i i o d i d e (13.9 g.), iodomethane (50.3 g.) and mercury (219.0 g.) were shaken for 30 days.  Extraction of the contents  of the tube with acetone gave 8.6 g. of yellow product which after r e c r y s t a l l i s a t i o n from acetone was i d e n t i f i e d as tetramethyl stibonium triiodomercury ( I I ) , m.p. Anal:-  Found:  C, 6*8;  H, 1*6;  167° ( y i e l d 417 ) . 0  Hg, 25'6;  I, 48»8%;  Hg, 26*3;  I, 49*8?  Calculated f o r (CH^SbHgl-j: C, 6*3;  H, 1*6;  0  The compound was insoluble i n camphor so no molecular weight measurement was made.  24 (ii)  Antimony T r i i o d i d e w i t h T r i f l u o r o i o d o m e t h a n e i n the Presence  of Mercury.  Antimony t r i i o d i d e fluoroiodomethane  (54.1  (14.9  g . ) , mercury (204.7 g.)  g.) were shaken f o r 30 days.  unreacted t r i f l u o r o i o d o m e t h a n e (54.0 (iii)  and  g.) was  tri-  Only  recovered.  D i i o d o p h e n y l s t i b i n e w i t h Iodomethane i n the Presence  of  Mercury. P h e n y l s t i b o n i c a c i d was  prepared by the r e a c t i o n of  d i a z o t i z e d a n i l i n e w i t h antimony t r i o x i d e (20).  The crude  s a l t C^H^SbCl^.NH^Cl.  was  p u r i f i e d through the double  was  converted t o d i i o d o p h e n y l s t i b i n e by r e a c t i n g w i t h stannous  c h l o r i d e i n the presence of sodium i o d i d e (20).  (20)|  and was  acid  The product  o b t a i n e d c o n s i s t e d o f orange y e l l o w c r y s t a l s m.p. 69°  The  oxide  69°  flit,  so value  kept under vacuum u n t i l needed.  D i i o d o p h e n y l s t i b i n e (8.0  g . ) , iodomethane (31.4  mercury (189.8 g.) were shaken f o r 40 days.  The  tube were e x t r a c t e d w i t h hot acetone and 15.6  g.)  and  contents o f the  g. o f a white  w i t h s l i g h t y e l l o w t i n g e c r y s t a l l i s e d from t h i s on c o o l i n g .  solid On  o r e c r y s t a l l i s a t i o n the s o l i d melted a t 147-148 as methylmercuric Anal:-  Found:  and was  identified  iodide.  C, 2*98; Mol. wt.  H, 0*74;  316, m.p.  Hg,  57*6;  I , 37.4%;  147°  CH^Hgl r e q u i r e s :  C, 3-5; Mol. wt.  H, 0-87; 343, m.p.  Hg, 58-6; 152° (8)  I , 37-0%;  25 A trace of yellow product was also obtained from t h i s reaction.  I t was not i d e n t i f i e d but could probably be phenyl-  trimethylstibonium triiodomercury ( I I ) . (iv)  Diiodophenylstibine with Trifluoroiodomethane  i n the  Presence of Mercury. Diiodophenylstibine (14.0 g.), mercury (201.4 g.), and trifluoroiodomethane  (43.8 g.) were shaken for 40 days at 20°.  The v o l a t i l e contents of the tube were taken into the vacuum system and found to contain only unreacted  trifluoroiodomethane.  The recovery was almost quantitative (43.2 g.). Similar reactions of iododiphenylstibine could not be studied as the iodostibine could not be prepared i n s u f f i c i e n t l y pure state.  When t r i p h e n y l s t i b i n e was converted to bis(diphenyl-  antimony) oxide (21), and the oxide was subsequently  converted to  chlorodiphenylstibine v i a the acetate, i t was found that the chloride could not be c r y s t a l l i s e d free from an accompanying gummy impurity, and hence was not suitable f o r preparing iododiphenylstibine by action of sodium iodide.  Renewed e f f o r t to  prepare pure chlorodiphenylstibine through tetraphenyl t i n (22) was not made due to limitations of time. (v)  Bismuth T r i i o d i d e with Trifluoroiodomethane  i n the Presence  of Mercury. Commercial bismuth t r i i o d i d e (19.7 g.), mercury (301.3 g.) and trifluoroiodomethane  (79.0 g.) were reacted f o r 15 days.  Amount of trifluoroiodomethane recovered was 77.3 g.  Probably  26 there was no reaction. (vi)  Bismuth T r i i o d i d e with Iodomethane i n the Presence of Mercury. Commercial bismuth t r i i o d i d e (22.2 g.), mercury (300 g.)  and iodomethane (63.2 g.) were shaken i n a sealed tube for 14 days.  The extract with acetone was yellow.  On c r y s t a l l i s a t i o n ,  the product appeared to decompose into mercuric iodide.  I t was  probable that the yellow solution contained only mercuric iodide and bismuth t r i i o d i d e i n solution. (vii)  Phosphorus T r i i o d i d e with Trifluoroiodomethane i n the Presence of Mercury. Commercial phosphorus t r i i o d i d e (18.0 g.), mercury (313.5 g.)  and trifluoroiodomethane (82.5 g.) were shaken for 50 days. T r a p - t o - t r a p - d i s t i l l a t i o n f a i l e d to i s o l a t e any trifluoromethyl compound other than the unreacted trifluoroiodomethane (83.0 g.). (viii)  Phosphorus T r i i o d i d e with Iodomethane  i n the Presence of  Mercury. Commercial phosphorus t r i i o d i d e (18.5 g.), mercury (214.8 g.) and iodomethane (65.2 g.) were shaken for 50 days.  Subsequent  extraction, c r y s t a l l i s a t i o n , and p u r i f i c a t i o n was found to be extremely d i f f i c u l t as the yellowish white product was only very s l i g h t l y soluble i n acetone and i n alcohol. insoluble i n other common solvents.  I t was also  A laborious manipulation  enabled separation of several fractions ranging i n m.p. 148° to 162°.  from  These fractions were mixed and r e c r y s t a l l i s e d from  27 o alcohol to give a product m.p.  165  o -170  ( y i e l d 6.0  g.).  A small amount of an impure o i l y (or waxy) yellow product m.p.  85-106° was  also obtained from t h i s reaction.  Analysis of  t h i s impure s o l i d approximates to C, 5;  H, 13;  P, 1*0;  Hg,  1*0;  I,  2-4.  On the basis that a l i k e l y reaction product would be a t e t r a methylphosphonium compound, the only known derivative of t h i s , (CH-p^PI^Hg]^, was prepared by mixing a l c o h o l i c solutions of 1 mole of tetramethylphosphomium iodide and 2 moles of mercuric iodide.  On r e c r y s t a l l i s i n g the yellow p r e c i p i t a t e  from alcohol, i t melted at 172°-175° [ l i t . value 172°  (23)J  .  However the mixed melting point of the 1:1 mixture of the yellow white reaction product and the reference compound was o 141  .  Moreover a comparison of t h e i r i n f r a r e d spectra confirmed  that they were not i d e n t i c a l .  I d e n t i f i c a t i o n was  rendered s t i l l  more d i f f i c u l t from the fact that the s o l i d f a i l e d to give a sharp X-ray powder pattern. C, 2-9;  H, 9*4;  Analysis of the product gave P, 1*0;  Hg,  approximated to the compound (CH^^PHg^. synthesis of t h i s compound was  l'l;  I, 2*4, which  Therefore the d i r e c t  attempted as follows.  Trimethyl phosphine for t h i s reaction was  prepared by  heating the s i l v e r iodide complex (CH^^P.Agl^, kindly supplied by Dr. M. A. Beg.  The evolved phosphine was  c o l l e c t e d i n a trap  of the vacuum system, cooled by l i q u i d nitrogen. (1.2776 g.; 1 mole) was  The phosphine  condensed onto mercuric iodide (7.6518 g.;  28 1 mole) i n a glass tube. 6 days.  The tube was  sealed and kept at 90° for  On opening the tube to the vacuum system no v o l a t i l e  product or unreacted phosphine was obtained. product, on infrared examination, was  The s o l i d yellowish  i d e n t i c a l with that  obtained i n the reaction of phosphorus t r i i o d i d e with iodomethane i n the presence of mercury. soluble i n acetone and i n alcohol.  I t was only very s l i g h t l y The product was  recrystal-  l i s e d using a very large volume of alcohol-acetone mixture (2:1 by volume), and 5.7 g. of pure product was obtained  m.p.  o 197-200 .  Analysis confirmed i t s i d e n t i t y as the 1:1 adduct of  trimethylphosphine and mercuric iodide. Anal:-  Found:  C, 6*9; Mol. wt.  H, 1*65;  Hg, 37'5;  I, 47*6;  P, 5*75%  Hg, 37*8;  I, 47*8;  P, 5«8%;  565  Calculated for ( C H ^ P . H g l ^ C, 6'8; Mol. wt.  H, 1'69; 531.  SECTION C Reactions of T e r t i a r y Arsine Complexes with Iodomethane, Trifluoroiodomethane and Iodoethane (i)  Reaction of the 1:1 complex of Diphenylmethylarsine and Mercuric Iodide with Iodomethane. The 1:1 adduct of diphenylmethylarsine and mercuric iodide  was prepared by reacting together a l c o h o l i c solutions of the arsine (2.9 g.; 1 mole) and mercuric iodide (5.4 g.; 1 mole).  29 P r e c i p i t a t e s were r e c r y s t a l l i s e d from a l c o h o l v a l u e 116  (24)]  The y i e l d was 3.3  .  or m.p.117 D - i t .  g. X-ray powder photograph  and i n f r a r e d spectrum were o b t a i n e d . The complex was r e a c t e d w i t h iodomethane i n two separate experiments. (a)  The complex (0.7  g.) and iodomethane (0.8  g.) were o  r e a c t e d i n acetone. was  A y e l l o w product  (0.72  g.) m e l t i n g a t 121  o b t a i n e d as a p r e c i p i t a t e . (b)  The complex (0.77 g.) and iodomethane (14.49 g.) were  s e a l e d i n a g l a s s tube. unreacted (0.8  The tube was opened a f t e r a week, and  iodomethane removed under vacuum. o  g.) m e l t i n g a t 122 The y e l l o w product  A yellow  product  was o b t a i n e d . i n both r e a c t i o n s was expected  t o be  diphenyldimethylarsonium  t r i i o d o m e r c u r y ( I I ) . On t h i s b a s i s o the y i e l d from these r e a c t i o n s was about 907o. The m.p. 122 appeared t o be somewhat d i f f e r e n t from the most probable  value  o 131  o f the same complex s y n t h e s i z e d e a r l i e r from the r e a c t i o n  of iodomethane w i t h i o d o d i p h e n y l a r s i n e i n the presence o f mercury.  However, i t was observed  reactions  (a) and (b) were r e c r y s t a l l i s e d from a l c o h o l , the m.p. o  was  r a i s e d t o 130  these products  .  t h a t i f thepproducts  o f these  F u r t h e r c o n f i r m a t i o n o f the i n d e n t i t y o f  from r e a c t i o n (a) and (b) w i t h t h a t o b t a i n e d i n  the r e a c t i o n o f iodomethane w i t h i o d o d i p h e n y l a r s i n e i n the p r e sence o f mercury was o b t a i n e d by t a k i n g mixed m e l t i n g p o i n t s and by comparing X-ray powder photographs.  30 (ii)  Reaction of the 2:1 Complex of Triphenylarsine and Mercuric Iodide with Iodomethane. The 2:1 adduat was prepared by reacting together a l c o h o l i c  solutions of triphenylarsine (2 moles) and mercuric iodide (1 mole). alcohol.  The product was p u r i f i e d by c r y s t a l l i s a t i o n from I t melted at 198°.  [ l i t . value 197° (13)]  The 2:1 complex (2.015 g.) and iodomethane (9.745 g.) were sealed i n a glass tube.  A f t e r one week, the unreacted iodo-  methane (8.803 g.) was removed under vacuum.  The amount of  iodomethane consumed i n t h i s reaction was 0.942 g.  The s o l i d 0  yellow residue (2.136 g.) l e f t i n the tube melted at 174 . I t was expected to be a bis(arsonium) tetraiodomercury (II) complex.  For i t s i d e n t i f i c a t i o n a reference compound b i s ( t r i o  phenylmethylarsonium) tetraiodomercury (II) m.p.  175  was pre-  pared by reacting alcoholic solutions of commercial t r i p h e n y l methylarsonium iodide and mercuric iodide i n correct proportions. The complex was r e c r y s t a l l i s e d from alcohol.  The analysis of  the reference compound gave C, 34*07;  H, 2*64;  Hg, 14«35%;  Mol. wt. 424.  The values calculated for ^(CgH^^AsCH-jj Hgl^ are C, 33*9;  H, 2*67;  Hg, 14*97 ; 0  Mol. wt. 1350.  A comparison of the infrared spectra and the melting points of the reference compound and the product of the reaction suggested that they were i d e n t i c a l . mixed melting point.  Confirmation was obtained by taking a  The y i e l d f o r the iodomethane addition  reaction was thus (iii)  84%.  Reaction of the 2:1 Complex of Triphenylarsine and Mercuric Iodide with Trifluoroiodomethane. The 2:1 complex (1.675 g.) and trifluoroiodomethane  (11.774 g.) were sealed under vacuum.  A f t e r six days, the tube  was opened to the vacuum system, and trap-to-trap d i s t i l l a t i o n of the v o l a t i l e contents of the tube, and infrared  examination  of the fractions i s o l a t e d , showed that only unreacted iodomethane (11.784 g.) was (iv)  trifluoro-  present.  Reaction of the 2:1 Complex of Triphenylarsine and Mercuric Iodide with Bromoethane. The 2:1 complex  (1.95 g.) and bromoethane (5.975 g.)  were sealed i n a tube which was opened after 18 days. amount of unreacted bromoethane recovered was  The  5.966 g., i n d i c a -  t i n g no reaction had occurred. (v)  Reaction of the 2:1 Complex of Triphenylarsine and Mercuric Iodide with Iodoethane. The 2:1 complex (2.725 g.) and 9.097 g. of iodoethane were  s i m i l a r l y reacted for 25 days.  I t was  found that only 0.223 g.  of iodoethane was consumed i n the r e a c t i o n . A d i r t y white s o l i d residue (2.783 g.) l e f t i n the tube melted between 89-97°. c r y s t a l l i s i n g from acetone i t was  fractionated into 0.914  a white product and 0.587 g. of a yellow product.  By g. of  The white o  product was r e c r y s t a l l i s e d from acetone when i t melted at 202 , and was  i d e n t i f i e d as unreacted s t a r t i n g material by comparison  32 of t h e i r infrared spectra and X-ray powder photographs. o The yellow product m.p. Anal:-  Found:  C, 29-4;  88  was  H, 2«57;  analysed. Hg, 20*3%.  Mol. wt.  751.  These results best f i t the compound (C^H^gAsC^H^Hgl-j. Calculated for ( C H ) A s C H H g I : 6  5  3  2  C, 28«4; (vi)  5  3  H, 1*97;  Hg, 21*9%.  Mol. wt.  917.  Reaction of the 1:1 Complex of Phenyldimethylarsine and Mercuric Iodide with Iodomethane. Phenyldimethylarsine was prepared by the action of iododi-  methylarsine on phenylmagnesium bromide i n ether (25), and  was  f i n a l l y p u r i f i e d by f r a c t i o n a l d i s t i l l a t i o n i n a small s t i l l provided with a fractionating column.  The 1:1 complex of the  arsine and mercuric iodide was prepared by mixing t h e i r a l c o h o l i c solutions i n molar proportions. dissolved i n alcohol.  The yellowish p r e c i p i t a t e s were  On c r y s t a l l i s i n g , the f i r s t crop was  orange yellow needles but was  contaminated  by another product of  yellowish white colour which separated mainly i n the second crop as small f i n e needles.  By careful fractionation from acetone  alcohol the two products were separated.  and  Orange yellow needles  on r e c r y s t a l l i s a t i o n from alcohol melted at 144° which agrees with the l i t e r a t u r e value of the m.p. 144° (24) .  for the 1:1 complex  The other product, small yellowish white needles,  melted at 89°. The 1:1 complex, and iodomethane (15.8 g.) were sealed i n a tube which was opened after 13 days and unreacted iodomethane  33 (15.1 g.) was recovered.  The residue was a yellow c r y s t a l l i n e  product which appeared to be p a r t i a l l y decomposed to mercuric iodide.  When r e c r y s t a l l i s e d from acetone-alcohol a s l i g h t l y o  decomposed product was obtained.  I t melted at 128-129  and was  i d e n t i f i e d as phenyltrimethylarsonium triiodomercury (II) (m.p.  128 , page 21).  (vii)  The y i e l d was 2.8 g. (about 43%).  Reaction of the 1:1 Complex of T r i e t h y l a r s i n e and Mercuric Iodide with Iodomethane. The 1:1 complex was prepared by adding 6.4 g. t r i e t h y l -  arsine to 36.0 g. of mercuric iodide i n 200 ml. of 12% K l solution.  Aquous layer was decanted o f f and the s o l i d p u r i f i e d  by d i l u t i n g the acetone solution with alcohol.  A s o l i d was  obtained, m.p. 88° [ l i t . value 87-88° (13)] . T r i e t h y l a r s i n e was prepared by the action of arsenic t r i c h l o r i d e on ethylmagnesium bromide (26). was  The ethereal layer  separated and d i s t i l l e d under a current of nitrogen at  760 mm.  The arsine boiled at 140° [ l i t . value 138-139° (26)].  The 1:1 complex (3.139 g.) and iodomethane (22.279 g.) were l e f t for 30 days.  The tube was opened into the vacuum system  and 20.934 g. of unreacted iodomethane was recovered. due, a yellow o i l , slowly s o l i d i f i e d .  The r e s i -  The amount of the s o l i d o  product was 3.871 g. and i t melted at 68 . When r e c r y s t a l l i s e d from acetone-alcohol mixture, two fractions were obtained. The less soluble yellowish white compound melted at 253° and weighed 1.533  g. The other, yellow f r a c t i o n was r e c r y s t a l l i s e d from  34 o alcohol. I t melted at 61 and weighed 0.903 g. For i d e n t i f i c a t i o n of these products, two reference compounds were f i r s t prepared.  Methyltriethylarsonium iodide was  prepared by mixing together t r i e t h y l a r s i n e and iodomethane i n 1:1 proportion. was  A f t e r r e c r y s t a l l i s a t i o n from alcohol the  m.p.  found to be 273° [ l i t . value 270° (27)] . From t h i s arsonium iodide two complexes triethylmethyl-  arsonium triiodomercury (II) and bis(triethylmethylarsonium) tetraiodomercury  (II) were prepared by mixing a l c o h o l i c solutions  of methyltriethylarsonium iodide and mercuric iodide i n calculated quantities (1:1 and 2:1 r e s p e c t i v e l y ) .  Both complexes were p u r i -  f i e d by r e c r y s t a l l i s a t i o n from a l c o h o l . The triethylmethylarsonium triiodomercury (II) thus prepared was yellow c r y s t a l l i n e and melted at 64°.  An analysis of  t h i s reference compound gave Found:  C, 11*26;  H, 2*39;  Hg, 26'07 ; o  Mol. wt.  793  Mol. wt.  759.  Calculated for ^ H ^ A s C l ^ H g l g : C, 11*1; The m.p.  H, 2-37;  Hg, 26»57 ; 0  (64°) of t h i s reference complex agrees with the  m.p.  o (61 ) of the yellow product obtained i n the above reaction. Their X-ray powder photographs also show good agreement. S i m i l a r l y the.reference complex bis(triethylmethylarsonium) tetraiodomercury ( I I ) ,  35 Anal:-  Found:  C, 15'89;  H, 3*34;  Hg, 18*55 %  Calculated for |(C H ) AsCH [ H g l : 2  5  3  C, 15»8;  3  4  H, 3*38;  Hg,  18*9%,  o agrees i n m.p.  (253 ) and X-ray powder photograph with the  yellowish white product obtained from the same r e a c t i o n . (viii)  Reaction of the 1:1 Complex of T r i e t h y l a r s i n e and Mercuric Iodide with Trifluoroiodomethane.  The complex (3.583 g.) and trifluoroiodomethane (16.595 g.) o were l e f t at 20  for 40 days.  The v o l a t i l e l i q u i d recovered  weighed 16.525 g., indicating there was no reaction. The experiment was repeated with 7.3 g. of complex and o 16.3 g. of trifluoroiodomethane at 100 for 48 hours. In t h i s case, the trifluoroiodomethane recovered weighed 15.9 g. A . o small f r a c t i o n (0.202 g.) condensed at (-98 ) and was  identified  as diethyltrifluoromethylarsine from i t s infrared spectrum (5). (ix)  Reaction of the 1:1 Complex of T r i e t h y l a r s i n e and Mercuric Iodide with Iodoethane. The complex (3.514 g.) and iodoethane  (6.428 g.) were  sealed i n a tube which was opened after 28 days. of iodoethane consumed i n t h i s reaction was  The quantity  found to be 0.654 g.  The product, a yellow s o l i d (2.710 g.), melted at 56°. By analogy with the corresponding reaction of the complex with iodomethane the product was  expected to be t e t r a e t h y l -  arsonium triiodomercury (II) (corresponding triethylmethylarsonium triiodomercury (II) melted at 61°).  However, a  36 comparison of X-ray powder photographs of (i) (ii) (iii)  the reaction product the s t a r t i n g (1:1) complex reference compound - tetraethylarsonium triiodomercury (II) (7)  (iv)  reference compound - bis(tetraethylarsonium) tetraiodomercury (II) (7)  convincingly showed that the closest resemblance was with the starting material.  From t h i s i t can be concluded that the yellow o  product melting at 56  was probably an impure s t a r t i n g complex  and i f there was any reaction, i t was only very i n s i g n i f i c a n t . SECTION D Reaction of Phenyldimethylarsine with  Trifluoroiodomethane  The preparation of phenyldimethylarsine has already been described, page 32. The arsine (6.3 g.) and trifluoroiodomethane (11.6 g.) were c a r e f u l l y sealed i n a tube under vacuum. apparent change was observed even after 22 days. o then kept at 100  No  The tube was  for 4 days and f i n a l l y opened to the vacuum  system, when 11.7 g. of a v o l a t i l e l i q u i d were recovered, indicating no reaction had occurred. The experiment was repeated with the arsine (2.2 g.) and trifluoroiodomethane (16.0 g.) keeping the tube at 170° for 12 hours.  Evidently there was some reaction t h i s time as the colour  had changed to dark brown.  The tube was opened to the vacuum  system and the v o l a t i l e contents removed leaving 0.8 g. of a  37 reddish v i o l e t s o l i d .  T h i s was  r e c r y s t a l l i s e d from a l c o h o l  and  o melted a t  93-98  .  I t was  probably  impure p h e n y l t r i m e t h y l -  103  arsonium t r i i o d i d e [ l i t . v a l u e m.p.  (12)J.  The v o l a t i l e m a t e r i a l on t r a p - t o - t r a p d i s t i l l a t i o n gave the f o l l o w i n g f r a c t i o n s : ( - 1 9 6 ° ] f r a c t i o n , 0.918  g. o f a mixture o f  and t r i f l u o r o i o d o m e t h a n e  fluoroform  i d e n t i f i e d by i t s i n f r a r e d  spectrum.  -  (-132°) f r a c t i o n , 12.9  g. o f  i d e n t i f i e d by i t s i n f r a r e d -  ^ — 9 8 ° ) f r a c t i o n , 1.045  trifluoroiodomethane, spectrum.  g. of a mixture c o n t a i n i n g  iodomethane, m e t h y l b i s t r i f l u o r o m e t h y l a r s i n e , benzotrifluoride  - (—46°) f r a c t i o n (1.1  - i d e n t i f i e d by i n f r a r e d  and  spectroscopy.  g . ) , i n f r a r e d examination showed  t h i s f r a c t i o n t o be a mixture o f methylarsine  and  phenylbistrifluoro-  methylphenyltrifluoromethylarsine.  TABLE - REACTIONS OF IODO-ARSINES AND ANALOGUES OF GROUP V Time of Reaction - Days  Reactants  Products  Yield  (C H ) AsI+CH I+Hg  21  (C H ) As(CH ) HgI  (C H )2AsI+C H I+Hg  21  (C H ) As(C H ) HgI  6  5  6  2  3  5  2  5  6  5  6  2  5  3  2  2  2  5  91%  3  2  3  and C H HgI 2  C H AsI 4CH I+Hg 6  5  2  3  18  4g.  5  C H As(CH ) HgI 6  5  3  3  44%  3  and CH HgI  37.6g.  3  C H5AsI 4C2H I-3-Hg 6  2  5  18  C H5As(C H ) HgI 6  2  5  3  3  and C H HgI 2  30 30  SbI +CF I+Hg 3  3  SbI -H:H I4flg 3  3  6  5  2  3  C H SbI 4X;H I+Hg 6  5  2  3  40 40  12.6g.  5  (CH ) SbHgI 4  3  CH HgI  15.6g.  and yellow product?  trace  BiI -rCF I4-Hg  15  BiI +CH I+Hg  14  PI +CF I+Hg  50  Nil  PI 4CH I+Hg  50  (CH ) P.HgI and impure  3  3  3  3  3  3  3  P(CH ) P-fHgI 3  3  2  6 at 90°  41%  Nil 3  3  33%  Nil 3  C H SbI -rCF I+Hg  >90%  Nil Nil  3  3  2  yellow waxy product  small  ( C s H ^ P H S ^ ••••)?  amount  (CH ) PHgI 3  3  2  64%  TABLE - REACTIONS OF TERTIARY ARSINE COMPLEXES Time of Reaction - Days  Reactants  Products  Yield  (C H ) As.CH HgI +CH I  7  (C H ) As(CH ) HgI  3  90%  {(C H ) As} -HgI +CH I  7  {(C H ) AsCH } Hgl4  84%  6  5  2  6  3  5  3  2  2  3  2  3  {(C H ) A s | .HgI +CF I 6  5  3  2  2  6  2  6  6  3  5  3  5  3  3  2  2  Nil  {(C H ) A s } .HgI 4€ H Br 6  5  3  2  2  2  5  18 {(C H ) As| .HgI +C H I 6  5  3  2  2  2  5  Nil  ;)  (C H ) AsC H HgI  *25  6  C H As(CH ) 'HgI +CH I  13  [{(C H ) As} (HgI ) ]  30  6  5  3  2  5  2  2  3  3  2  2  5  3  (C H ) AsCH HgI  3  3  5  3  3  3  3  43% 0.9g,  and {(C H ) AsCH } HgI 2  [{(C H ) As] (HgI ) J 3  2  5  2  3  5  3  C H As(CH ) HgI 6  4- CH I  2  5  2  2  3  3  2  4  1. • 5g.  Nil  40  2  5  + CF I 3  2 at 100°  [{(C H ) AsJ (HgI ) J 2  5  3  2  2  2  (C H ) AsCF 2  5  2  0.202g.  3  + CF I 3  (C H ) As} (HgI ) J 2  5  3  2  2  28  2  Probably no reaction  ft  + C H I 2  5  C H As(CH ) + C F I 6  5  3  2  C H,As(CH ) -hCf I 6  3  2  i  C H^As(CH3\-t-C^l 6  22  3  ^  4  i  2  1 Q O  ^  Nil  o ^  N  C  n  6  H  5  A  s  (  C  H  3  )  3  ]  -  3  >  C  F  3  H  j  170° CH I, (CF ) AsCH , 3  3  2  3  C H .CF , C H As.CF (CH ) 6  5  3  6  C H AS(CF ) 6  5  3  2  5  3  3  40 BIBLIOGRAPHY 1.  W. R. Cullen.  Can. J . Chem., 38., 439 (1960).  2.  W. R. Cullen.  Can. J . Chem., 38, 445 (1960).  3.  F. W. Bennet, H. J . Emeleus and R. N. Haszeldine. J . Chem. S o c , 1565 (1953).  4.  G. R. Brandt, H. J . Emeleus and R. N. Haszeldine. J . Chem. S o c , 2552 (1952).  5.  W. R. Cullen - Private communications  6.  H. J . Cavel and S. Sugden.  7.  M. M. Baig and W. R.' Cullen.  8.  E. Krause and Von Grosse - Die Chemie der Metal-Organischen Verbindungen.  9.  J . Chem. S o c , 2572 (1930). Can. J . Chem., 39, 420 (1961).  Borntraeger, B e r l i n (1937).  R. C. Cass, G. E. Coates and R. G. Hayter.  J . Chem. S o c ,  4007 (1955). 10. F. F. Blicke and F. D. Smith.  J . Am. Chem. S o c , 5_1,  2272 (1929). 11. F. F. Blicke and F. D. Smith.  J . Am. Chem. S o c , 52,  2937 (1930). 12. W. Steinkopf and G. Schwen.  Ber., 54B, 1437 (1921).  13. R. C. Evans, F. G. Mann, H. S. Peiser and D. Purdie. J . Chem. S o c , 1209 (1940). 14. A. E. Godard - A Text Book of Inorganic Chemistry, Edited by J . N. Friend. London (1930), page 87.  V o l . XI.  Charles G r i f f i n and Company,  41 15.  H. J . Emeleus and J . J . Lagowski.  J . Chem. S o c , 1497  (1959). 16.  R. N. Haszeldine and B. 0. West.  J . Chem. S o c , 3631  (1956). 17.  W. J . Pope and E. E. Turner.  18.  F. F. Blicke and F. D. Smith. 1558  19.  J . Chem. S o c , 1447 (1920). J . Am. Chem. S o c , 51,  (1929).  B a i l a r and Cundy - Inorganic Synthesis. H. S. Booth.  V o l . I, Edited by  McGraw-Hill Book Company (1939), page 104.  20.  Hans Schmidt.  Ann., 421, 174 (1920).  21.  Hans Schmidt.  Ann., 429, 123 (1922).  22.  Z. M. Manulkin, A. N. Tatarenko and F. Yu. Yusupov. Doklady Akad. Nauk. S.S.R., 88, 687 (1953).  23.  G. M. Kosoldpoff - Organophosphorus Compounds, John Wiley and Sons, New York (1950).  24.  J . J . Anderson and G. J . Burrows.  J . Proc. Roy. Soc.  N. S. Wales, 70, 63 (1936). 25.  G. J . Burrows and E. E. Turner.  26.  W. J . C. Dyke and W. J . Jones.  27.  W. J . C. Dyke, G. Davies and W. J . Jones. 185 (1931).  J . Chem. S o c , 1373 (1920). J . Chem. S o c , 2426 (1930). J . Chem. S o c ,  

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