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Trifluoromethanesulfonates of iodine Dalziel, John R. 1975

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TRIFLUOROMETHANESULFONATES OF IODINE  by  •  JOHN R. DALZIEL  B.Sc. (Hons.)* U n i v e r s i t y of B r i t i s h Columbia, 1  A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE  i n the Department of CHEMISTRY  We accept t h i s t h e s i s as conforming to the required standard  THE UNIVERSITY OF BRITISH COLUMBIA May, 1975  In  presenting  an  advanced  the I  Library  further  for  this  degree shall  agree  scholarly  by  his  of  this  written  thesis  in  at  University  the  make  that  it  may  representatives. for  freely  permission  purposes  thesis  partial  be  It  financial  for  gain  Depa rtment  The  University  Date  8,  of  British  Canada  of  Columbia,  British  Columbia  for  extensive by  the  understood  permission.  Vancouver  of  available  granted  is  fulfilment  shall  Head  be  requirements  reference copying  that  not  the  of  agree  and  of my  I  this  or  allowed  without  that  study. thesis  Department  copying  for  or  publication my  ii  Abstract The i n v e s t i g a t i o n of iodine trifluoromethanesulfonates was i n i t i a t e d by the synthesis of I ( S 0 C F ) 3  3  3  v i a the r e a c t i o n :  HSO-CFI  + 6HS0 CF + 3 S 0 F  2  3  3  2  6  —4>  2  2I(S0 CF ) 3  3  + 6HS0 F  3  3  I s o l a t i o n of i o d i n e ( I I I ) t r i s t r i f l u o r o m e t h a n e s u l f o n a t e was p o s s i b l e because of the very low s o l u b i l i t y of the compounds i n the a c i d mixture. The yellow white s o l i d proved to be free of f l u o r o s u l f a t e . The compound was used subsequently i n the synthesis of s a l t s of the general formula, M [ I ( S 0 C F ) ] , with M = K, Rb, or Cs, using HS0 CF I  3  3  1  4  as the reaction medium.  3  3  A l t e r n a t e routes to the t e t r a k i s  (trifluoro-  methanesulfonate) i o d a t e ( I I I ) compounds were also r e a l i z e d . Reduction of I ( S 0 C F ) 3  3  3  by an equimolar amount of I  2  at elevated  temperature i n a sealed tube r e s u l t e d in the formation of i o d i n e ( I ) trifluoromethanesulfonate.  Poly iodine compounds of the type ^ 0 3 ^ 3  with n = 3 , 5 or 7 could not be obtained. The a d d i t i o n of B r  2  to IS0* CF 3  resulted in the formation of the  3  dibromoiodonium t r i f l u o r o m e t h a n e s u l f o n a t e , I B r S 0 C F . 2  3  Other t r i a t o m i c  3  interhalogen polyhalogen cations such as ICl* or I*.could only be produced in s o l u t i o n s of  HSO-JCF-J.  The s o l v o l y s i s of IS0 CF 3  found to lead to blue s o l u t i o n s containing the- I  2  +  in HS0 CF was  3  3  3  cation.  Attempts to prepare abromine(III) trifluoromethanesulfonate  via  three d i f f e r e n t routes, s o l v o l y s i s of BrS0 F in HS0 CF , s o l v o l y s i s 3  BrF  3  in HS0 CF and oxidation of B r  successful. mixture.  3  3  2  3  3  of  in HS0 CF with S 0 g F , were un3  3  2  2  The usual r e s u l t was a v i o l e n t detonation of the reaction  iii  The synthesis of iodyl trifTuoromethanesul fonate, effected by reacting H I 0 3  methanesul fonate  g  and HS0 CF . 3  was obtained from  IC^SOgCF^was  S i m i l a r l y iodosyl  3  and H I 0 3  g  i n HSOgCFg.  trifTuoroBased on  the r e s u l t s of v i b r a t i o n a l spectroscopy, IOSO^CF^ i s thought to be made up of d i s c r e t e 10 units bridged by SO^CF^ groups. Structural studies based on i n f r a r e d and Raman spectroscopy were undertaken on a l l the products mentioned.  In addition the previously  synthesized compound CF^SO^CF^ was also studied as an example of a monodentate SOoCF- group.  iv  TABLE OF CONTENTS PAGE Abstract  ii  Table of Contents  iv  L i s t of Tables L i s t of Figures Acknowledgements CHAPTER I  II  INTRODUCTION  1  A.  The interhalogens  4  B.  Pclyhal.ides and P o s i t i v e Polyhalogen Complexes  6  C.  Halogen Oxyacid Compounds  9  D.  Trifluoromethanesulfonic a c i d and i t s d e r i v a t i v e s  10  EXPERIMENTAL  15  A.  15  Chemicals 1. Reagents a.  Commercial  15  b.  Prepared  16  2. Products a.  I o d i n e ( I I I ) and Iodine(I) t r i f l u r o m e t h a n e sulfonates  18  A l k a l i metal t e t r a k i s trifluoromethanesulfonate i o d a t e ( I I I ) s a l t s -  19  c.  Iodyl and Iodosyl trifluoromethanesulfonate  19  d.  Dihalo iodine trifluoromethane sulfonate  20  b.  continued  V  TABLE OF CONTENTS, Continued. PAGE B.  C.  III  Apparatus  21  1. Vacuum 1ines  21  2. Metal Fluorine Line  22  3 . Dry Atmosphere Box  22  4. Reactors  22  5. Miscellaneous  25  Spectrophotometers  28  1. Infared Spectrometer  28  2. Raman Spectrophotometer  28  3 . V i s i b l e and U l t r a v i o l e t Spectrophotometer  29  RESULTS AND DISCUSSION  30  A.  Introduction  30  B.  Synthesis  30  1. I o d i n e ( I I I ) t r i s t r i f l u o r o m e t h a n e s u l f o n a t e  30  2. I ( S 0 C F ) 2 c a t i o n  37  3  3.  C.  3  A l k a l i metal t e t r a k i s ( t r i f l u o r o m e t h a n e s u l f o n a t e ) iodate(III)  37  4. Iodine monokistrifluoromethanesulfonate o 5. Polyhalogen and Interhalogen trifluromethane sulfonates  39  6. Iodine-Oxygen trifluoromethanesulfonates  46  7. Bromine t r i s t r i f l u o r o m e t h a n e s u l f o n a t e  50  V i b r a t i o n a l Spectroscopy  52  1. General Introduction  52  2. M [ I ( S 0 C F ) ]  59  3  3  4  42  conti nued  TABLE OF CONTENTS, Continued.  3.  I(S0 CF )  4.  IS0 CF  5.  IBr S0 CF  6.  I0 S0 CF  3  3  3  2  3  3  2  3  7. I0S0 CF 3  IV  3  3  3  3  8. C F S 0 C F 3  3  3  GENERAL CONCLUSIONS  vi i  LIST OF TABLES  Table  PAGE  1  A l l red Rochow E l e c t r o n e g a t i v i t i e s f o r Selected Elements  3  2  AG° (Kcal/mole) f o r the Interhalogens  5  3  C a t i o n i c Compounds of Oxyacids  11  4  Elemental A n a l y s i s and Melting Points  36  5  A comparison of S0 X i n f r a r e d v i b r a t i o n a l frequencies i n (C H5) S n ( S 0 F ) and ( C H ) S n ( S 0 C F ) 3  2  2  3  2  2  5  2  3  3  58  2  6  V i b r a t i o n a l Frequencies f o r R b [ I ( S 0 C F ) ] and (CH ) GeS0 CF  7  V i b r a t i o n a l Spectrum of I ( S 0 C F )  8  V i b r a t i o n a l Spectrum of IS0 CF  9  Infrared Spectra of I B r S 0 C F  3  3  3  3  2  3  3  4  3  3  3  60 65  3  67  3  and AgS0 CF  3  3  3  69  3  10  V i b r a t i o n a l Frequencies f o r I B r  i n IBrS0 CF  11  V i b r a t i o n a l frequencies f o r I 0 S 0 C F  12  V i b r a t i o n a l Frequencies f o r I0S0 CF  13  1-0 S t r e t c h i n g Frequencies i n Several Compounds  79  14  V i b r a t i o n a l Spectra of C F S 0 C F  81  15  S-0 Stretching Frequencies i n i o n i c , monodentate, and bidentate S0 F and S 0 C F groups  2  3  2  3  3  3  3  3  3  3  3  3  and I B r S 0 F 2  and I 0 S 0 F 2  3  3  3  3  71 73 77  83  viii  LIST OF FIGURES Figure  PAGE  1  The Structure of [ I C l ^ l L S b C l g ]  8  2  Metal Fluorine l i n e  23  3  Pyrex Glass Reactors  26  4  Monel Metal Reactor  27  5  The System  41  6  C o r r e l a t i o n Diagram of SO^X  7  Normal Vibrations of SO3CF3 groups with C3 Symmetry  55  8  Raman Spectrum of USO^CF^)^  63  9  Infrared Spectra of (10 JSO^CF^ and ( I 0 ) S 0 C F  -  ^ ^ O ^  53 V  2  3  3  from 1500-250 cm"  1  75  ix Acknowledgements I would l i k e to acknowledge my extreme indebtedness to Dr. Aubke f o r his supervision throughout the course of t h i s work.  F.  From  i t s inception to i t s completion his suggestions and encouragement have been of immeasurable h e l p .  I w i l l never be able to express f u l l y the  gratitude that he deserves. I would also l i k e to thank a l l of my coworkers i n Lab. 457 f o r t h e i r f r i e n d s h i p and a s s i s t a n c e , without them the l a s t four years would not have been as pleasant as they were. F i n a l l y I would l i k e to thank a l l those who taught me Chemistry, p a r t i c u l a r l y Dr. R.F. Grant, who when I was considering many a l t e r n a t e professions made my f i r s t year of Chemistry the f i r s t of many.  Introduction From a f i r s t year general chemistry text the f o l l o w i n g d e s c r i p t i o n of the halogens i s t a k e n : 1  "The halogen atoms a l l have seven electrons in t h e i r outer s h e l l and are f o l l o w e d , i n each case, i n the p e r i o d i c t a b l e by a noble gas. Consequently t h e i r most s t a b l e o x i d a t i o n number i s - 1 . A l l the halogens except f l u o r i n e are known to e x i s t i n several o x i d a t i o n s t a t e s . " This preliminary d e f i n i t i o n i s followed by a d e s c r i p t i v e chemistry of the halogens which i s e x c l u s i v e l y the chemistry of the h a l i d e s , X~.  Most  f i r s t year chemistry students when asked to describe the chemistry of the halogens respond with a d e s c r i p t i o n of h a l i d e chemistry.  Very few are  aware of the p o s i t i v e character which a l l halogens except f l u o r i n e can and do d i s p l a y .  Since the compounds synthesized here are a l l c a t i o n i c  halogen compounds, a short i n t r o d u c t i o n of the subject i s i n order. C a t i o n i c halogen compounds are ones in which the halogen X can be considered to have a p o s i t i v e o x i d a t i o n number, e i t h e r 1 , 3 , 5 or 7 and to occupy f o r m a l l y a c a t i o n i c p o s i t i o n .  An example i s c h l o r i n e n i t r a t e ,  ClN0\j, where i n analogy to potassium n i t r a t e KNO^ the c h l o r i n e occupies the c a t i o n i c p o s i t i o n .  In general the halogen w i l l not e x i s t as a true  cation as found in an i o n i c compound but rather i t w i l l be the p o s i t i v e l y p o l a r i z e d part of a covalent molecule of general formula x - y~ or in 6 + 6 the example CI - ONC^ rather than K NO^". There are several important +  consequences of t h i s covalent nature of c a t i o n i c halogen compounds which may r e s u l t : a)  The compounds may be v o l a t i l e , in p a r t i c u l a r when the halogen  is chlorine.  2. b)  The symmetry of the "anion" may be reduced ( e . g .  for NOj  Ufo to C^y or even lower)  C. )  hydrolysis of the compound w i l l be complex r e s u l t i n g i n  more than j u s t simple ion formation. H0 -—-Na HO -2H 2  e.g.  NaNCL C1N0  3  +  ( s o l v ) + NO+  (solv)  (1)  ( s o l v ) + N 0 ' CIO"  (2)  3  The halogen most l i k e l y to form c a t i o n i c halogen compounds i s  * iodine (with the possible exception of a s t a t i n e ).  This i s apparent from  the e l e c t r o n e g a t i v i t i e s of the halogens l i s t e d i n table 1.  On purely  e l e c t r o n e g a t i v i t y grounds p o s i t i v e l y p o l a r i z e d iodine i s expected f o r bonds with the f o l l o w i n g :  the halogens B r , CI and F; the chalcogenides  Se, S and 0 ; the group V element N and the group IV element C. bromine and c h l o r i n e only F, 0 and N remain as p o t e n t i a l F l u o r i n e , as expected from i t s e l e c t r o n e g a t i v i t y  For  partners.  has not been found to  form any c a t i o n i c halogen compounds. In s p i t e of a wide array of p o s s i b l e anion sources in p r a c t i c e only oxygen, the halogens themselves, and a to a l i m i t e d extent have been found to produce binary c a t i o n i c halogen compounds.  nitrogen The com-  pounds are the i n t e r n a l o g e n s , halogen o x i d e s , and halogen n i t r i d e s .  Only  the f i r s t two categories w i l l be d i s c u s s e d .  *  A s t a t i n e should have a greater c a t i o n i c tendency than Iodine,.however, i t s very short h a l f l i f e , only 8.3 hours f o r the most stable i s o t o p e , has prevented any d e t a i l e d chemical i n v e s t i g a t i o n .  TABLE 1 Allred-Rochow E l e c t r o n e g a t i v i t i e s  Group  IV A  V A  C  N  2.50  f o r selected Elements  VI A 0  3.07 P 2.06  3.50 S  VII A F 4.10 CI  2.44  2.83  Se  Br  2.48  2.74 I 2.21  Values taken from:  J . Inorg. N u c l . Chem., 5_, 264 (.1958).  4.  A.  The interhalogens The general formula f o r any interhalogen i s XY when Y i s always n  the l i g h t e r halogen and n i s odd, e i t h e r 1 , 3 , 5 or 7.  In a l l , 13 i n t e r -  halogens are known to be s t a b l e and are l i s t e d in t a b l e 2. f l u o r i n e only acts as the Y group.  Note that  The majority of interhalogen com-  pounds are halogen f l u o r i d e s . Iodine i s the c a t i o n i c halogen f o r the l a r g e s t number of interhalogens and i t e x h i b i t s i t s highest o x i d a t i o n number, +7 with f l u o r i n e .  A l l these are expected from the e l e c t r o n e g a -  t i v i t y arguments. The thermal s t a b i l i t y of the diatomic i n t e r h a l o g e n s , XY, i s due to a combination o f two main f a c t o r s . bond energy of the X-Y bond.  F i r s t there i s the i n t r i n s i c  This can be estimated from the standard  free energies AG° given i n t a b l e 2.  Second there i s the tendency f o r  XY to undergo d i s p r o p o r t i o n a t e i n t o nX  2  and  x v  (2n+l)'  This tendency  i s apparent from the AG of r e a c t i o n and i s i n d i c a t e d by an increased AG° of the products.  From thermodynamic data and measured or estimated 2  bond energy values accumulated by Wiebenga et a l .  i t can be seen t h a t ,  although the bond energies f o r XY were l e s s f o r the l i g h t e r c a t i o n i c , X, halogens, the corresponding XY^ and XY^ compounds were a l s o much less s t a b l e . i.e.  For the diatomic f l u o r i d e s formed from the heavier halogens,  IF,the greater s t a b i l i t y of IF,- and IF^ e f f e c t i v e l y n u l l i f i e d the  s t a b i l i t y f a c t o r of the high bond energy f o r 5IF 7IF  AG*=  r3%Z  IF.  Kcal  (3)  Kcal  (4)  5.  TABLE 2 AG°f(Kcal/mole) f o r the Interhalogens'  X CI Br  c l F  (g)  B r F  (g)  B r C 1  I  AG  XY  (g)  I F  (g)  I C  '(s)  I B r  (s)  0 X Y  AG°  3  X Y  5  AG°  XY  -13.4  ClF (g)  -38.8  ClF (g)  -  -  -14.7  BrF (l)  -75  BrF (l)  -127.5  -  -  --  3  3  -  -3.46  -  -22.7  I F  -7.67  ICl (s)  -"  3 3  -  -21.1  -  5  5  IF (1) S  -  7  -205.3  -  I F  7(g)  -  -  AG  C  6. As a r e s u l t , while the order of s t a b i l i t y f o r the binary interhalogens with respect to the elements i s IF > BrF > C1F >IC1  7 IBr > B r C l , iodine  monofluoride which has supposedly the most s t a b l e bond  has been detected  only in flames where iodine i s brought i n t o contact with f l u o r i n e . i s at high temperatures where I-F  bonds are cleaved quite r e a d i l y and  the d i s p r o p o r t i o n a t e reactions mentioned above do not occur  B.  That  irreversibly.  Polyhalides and P o s i t i v e Polyhalogen Complexes Interhalogens are c l o s e l y r e l a t e d to two kinds of i o n s ; the p o l y -  h a l i d e anions, and the polyhalogen c a t i o n s . An interhalogen such as BrF^ can act as a halide ion acceptor to form a polyhalide a n i o n , BrF^", or a h a l i d e ion donor to form a p o l y halogen c a t i o n , B r F BrF  . 2  2  +  SbF " 6  according to excess SbF,2.  B  rF  KF 3  »-K BrF^"  (5) - 3  Except f o r short l i v e d r a d i c a l s such as C l  2  and FC1  polyhalogen  anions are diamagnetic and thus contain generally an odd number of atoms. In the exceptions, the even polyhalides i . e . C s l ^ the observed diamagnetism i n d i c a t e s that at l e a s t two empirical u n i t s make up the real formula. This has been confirmed by X-ray d i f f r a c t i o n s t u d i e s ^ .  The chemistry,  s t r u c t u r e , and bonding of p o l y h a l i d e anions has been reviewed r e c e n t l y by 5 Popov  and s h a l l not be discussed f u r t h e r . Polyhalogen c a t i o n s , as shown by the above example (eq. 5 ) ,  may be formed from the neutral interhalogens on i n t e r a c t i o n with strong Lewis acids such as SbF^. or Al CI neutral i n t e r h a l o g e n .  Recently  3  e f f e c t i n g halide ion t r a n s f e r from the some f l u o r o s u l f a t e s with t r i a t o m i c  cations of the type IX,,  or  (with X = CI or B r ) , have been reported,  suggesting an a l t e r n a t e route to i n t e r - and polyhalogen c a t i o n i c compounds.  D e t a i l s w i l l be discussed l a t e r . A word of caution i s necessary regarding the use of the term  " c a t i o n " in r e f e r r i n g to these i n t e r - and poly-halogen compounds. From the bond distances f o r I C l - S b C l g 2  7  given i n f i g u r e 1 i t can be  seen that the use of the term cation f o r the ICl^ moiety i s somewhat misleading because appreciable a n i o n - c a t i o n i n t e r a c t i o n i s present. In t h i s case the i n t e r a c t i o n involved c h l o r i n e bridges which r e s u l t i n a d i s t o r t e d anion and a polymeric s t r u c t u r e .  The true s t r u c t u r e  is  somewhere between a genuine i o n i c s o l i d and a two dimensional polymer. Anion cation i n t e r a c t i o n s of varying degrees have been found f o r a l l compounds of t h i s type. g structure analysis  They are most e a s i l y detected by X-ray  but are also apparent from v i b r a t i o n a l  9 analysis  spectral  10 or from N.Q.R. studies  .  The observed a n i o n - c a t i o n i n t e r -  action i n the s o l i d s t a t e may be broken up by d i s s o l v i n g the compound i n strong protonic a c i d s ,  e.g.:  HSO3F B r F SbF 2 6 0  c  -BrF  , . * + SbF ~, , ^ 2 (solv) 6 (solv)  0  c  In summary, whereas monoatomic halogen cations of the type X + are  nonexistent, polyhalogen or interhalogen cations X  exist.  n  +  + or  XY  do  n  However, some degree of a n i o n i c - c a t i o n i c a s s o c i a t i o n i n the  s o l i d state and s t a b i l i z a t i o n by s u i t a b l e strong protonic acids i n s o l u t i o n i s necessary f o r t h e i r e x i s t e n c e . An a d d i t i o n a l group of compounds e x i s t where a p o s i t i v e l y halogen i s s t a b i l i z e d by Lewis b a s e s  11  charged  such as pyridine or q u i n o l i n e .  The Structure of [iCl^fSbClg]  a 2.26  •Cl  4  2.34  116.8 V..  3.00'*.. ^ 8 5 J 0 ?  f\  CI8  N  /2.85  A  913° J_ 68.7° '  Cl,  Cl;  9.  These compounds, commonly c a l l e d s t a b i l i z e d halogen compounds are obtained by r e a c t i o n such as I  2  + AgN0  +  3  Zpy  ^  -Agl + [I(py) ] 2  (7)  [NO3]  where the d r i v i n g force of the reaction i s the formation of the i n s o l u b l e silver salt. C.  They are mentioned here f o r the sake of completeness.  Halogen Oxyacid Compounds Of greater relevance to t h i s study are halogen oxy d e r i v a t i v e s 12  of oxyacids such as I0(N0 )  They have been known f o r a long time 13 and were commonly r e f e r r e d to as basic s a l t s . For example, as shown 14 recently by T. K i k i n d a i the i n t e r a c t i o n product between fuming n i t r i c acid and I i s best regarded as IONO^. This compound was o r i g i n a l l y 3  .  2  12 obtained by M. Mi 11 on  . and I^O^ have long been forumlated as  The oxides of iodine iodosyl and iodyl i o d a t e s .  These and r e l a t e d compounds such as the  iodosyl d e r i v a t i v e s of H S0^ and H SeO^ are well s t u d i e d . 2  2  Although bromine oxygen analogues to 10 and I 0  2  compounds appear  to be thermally unstable, some c h l o r i n e oxygen compounds containing the 15 c h l o r y l group, C10 are known. 2  Compounds such as C10,,S0 F 3  and  16 (C10 ) S 0-|Q 2  2  3  , i n marked contrast to the highly polymeric I 0  2  compounds,  are found to be s o l u b l e i n strong a c i d s , and produce q u a n t i t a t i v e l y the chloronium c a t i o n C 1 0 . 2  +  Generally iodine (III)  compounds as  well as i o d y l , I 0 , and 2  i o d o s y l , 10, compounds are formed by a number of strong to medium strong acids such as the monobasic oxyacids, H0 CCF 2  basic acids l i k e H S 0 2  4  3  and HN0 and i n c l u d i n g d i 3  and H,,Se0 and even t r i basic H-^PO^. 4  10. As can be seen from t a b l e 3 , the formation of Br(I) and CI(I)  oxyacid d e r i v a t i v e s are r e s t r i c t e d to r e l a t i v e l y strong mono-  basic a c i d s . made. IF  5  and Br(111)  F i n a l l y , only one s t a b l e 1(1) d e r i v a t i v e , ISO^F, has been  It seems that i n analogy to the d i s p r o p o r t i o n a t e of IF i n t o  and ^ e q u a t i o n t h a t the I (111) compounds are thermodynamically v  favoured. There i s a r i c h chemistry of p o s i t i v e halogens.  Of the halogens,  iodine has the most extensive chemistry i n c l u d i n g binary oxyacid d e r i vatives.  The occurrence of c a t i o n i c halogen compounds appears to  be connected with the a c i d strength of the given oxyacid.  A brief dis-  cussion of HSO^CFg, the a c i d used i n t h i s work, f o l l o w s .  D.  Trifluoromethanesulfonic A c i d and i t s  Derivatives  Trifluoromethanesulfonic a c i d i s a strong monobasic protonic acid.  It was o r i g i n a l l y prepared i n 1 9 5 4  (trifluoromethylthio)  17  by the o x i d a t i o n of b i s  mercury and p u r i f i e d by treatment of barium b i s  trifluoromethanesulfonate with  fuming s u l f u r i c a c i d .  not p r a c t i c a b l e f o r producing large q u a n t i t i e s .  This method i s  HSO^CF^ i s now manu-  factured commercially by the e l e c t r o f l u o r i n a t i o n of CH2SO2CI and d i s t r i b u t e d as Fluorochemical Acid by the Minnesota Mining and Manufact u r i n g Company.  In respect to acid strength t r i f l u o r o m e t h a n e s u l f o n i c 14  a c i d has been claimed to be the strongest monobasic acid known based on the c o n d u c t i v i t i e s of various acids i n a c e t i c a c i d .  On the  other hand, HSO^CF^ reacts with organotin compounds in much the same 1g manner as HSO^F . The r e s u l t i n g organotinsulfonates are i s o s t r u c t u r a l  11  TABLE 3 C a t i o n i c Compounds of Oxyacids  Acids H^Y  Groups  Compounds formed by Oxyacids and Halogens Group 1  CH C00H 3  IY  3  CFgCOOH  IOY  H S0  4  I0 Y  H P0  4  2  3  2  H Se0  4  Group 2 C1Y  H Te0  4  BrY  2  2  HOTeFr-  1 2  H0SeF  1 2  HN0  1 2  3  HC10  4  HS0 F 3  e  BrY,  Group 3  IY  1 2  ¥  1 2 3  IX Y 2  CX=C1 or Br)  12. and have completely i d e n t i c a l  •£< Sn Mossbauer parameters.  It,  there-  f o r e , seems reasonable to assume HSO^CF^ i s as strong an acid as HSO^F or HC10 .  Some physical properties of HS0 CF would i n d i c a t e t h i s .  4  3  A b r i e f review of the chemistry of HS0 CF 3  3  3  up to 1965 has been given  k c • 19 by Senmng  No d e t a i l e d s t r u c t u r a l studies ( e . g . X-ray d i f f r a c t i o n )  of  t r i f l u o r o m e t h a n e s u l f o n i c a c i d d e r i v a t i v e s have been undertaken.  How-  ever, there are two i n f r a r e d and Raman studies i n v o l v i n g normal c o 20 21 ordinate analyses and force f i e l d c a l c u l a t i o n s on the S 0 C F 3  3  anion  '  The problem of assigning bands i s complicated by a near coincidence of CF  3  and S 0 v i b r a t i o n a l modes and extensive v i b r a t i o n a l mixing of  modes.  3  The proposed assignments in the two studies d i f f e r w i d e l y . The trifluoromethanesulfonate group can act as a monodentate,  b i d e n t a t e , or even t r i d e n t a t e l i g a n d through oxygen. metal s a l t s the S0 CF 3  3  In the a l k a l i  group i s an anion S0 CF ~ while i n the t i t an i u m 3  3  chloro s a l t s i t acts as a bidentate l i g an d in T i C ^ S O - j C F . ^ or a 22 tridentate ligand in T i C l S 0 C F . In a manner s i m i l a r to the f l u o r o 22 23 3  3  3  s u l f a t e s of t i t a n i a m and t i n bidentate or t r i d e n t a t e S 0 C F 3  ' 3  the trifluoromethanesulfonates have groups which act as bridging ligands  rather than as c h e l a t i n g groups. In Organic chemistry the a c i d strength of HS0 CF 3  i n s i t u a t i o n s where p e r c h l o r i c acid has been used.  3  is utilized  In t h i s  respect  t r i f l u o r o m e t h a n e s u l f o n i c acid i s of comparable strength but i s not nearly such a strong o x i d i z e r and i t s use reduces hazards. of t h i s use a r e ; f i r s t , the use of HS0 CF 3  3  Two examples  as a t i t r a n t i n g l a c i a l  13. acetic acid solution  24  and second, as a replacement f o r HCIO^ when a  strongly a c i d i c media i s r e q u i r e d .  In organic syntheses the SO3CF3  group i s a good l e a v i n g group, and i n e l e c t r o c h e m i s t r y the weakly coo r d i n a t i n g properties of the SO^CF^" ion make i t a good a l t e r n a t i v e to the perchlorate ion as a support e l e c t r o l y t e . That t r i f l u o r o m e t h a n e s u l f o n i c a c i d has been i n v e s t i g a t e d because of i t s s i m i l a r i t y to other strong a c i d s , at l e a s t in p a r t , i s 25 26 borne out by several authors who have used the properties of HSO^F ' , ?4 HC10  4  27 and H S 0 2  to argue the f e a s a b i l i t y of HS0 CF . 3  4  3  However,  even when the s i m i l a r i t y of HS0 CF to other strong acids i s the 3  3  reason f o r i t s i n v e s t i g a t i o n , i t i s the unique c h a r a c t e r i s t i c s of the a c i d which are most important.  For example, as a strong a c i d media  instead of HC10 , i t i s the o x i d a t i v e s t a b i l i t y of HS0 CF which i s 3  4  3  so v a l u a b l e , while i n t i t r a t i o n s in a c e t i c a c i d the non formation of gels with potassium hydrogen p^thal'ate i s important. Trifluoromethanesulfonic a c i d fumes on contact with a i r and reacts with moisture to form a s t a b l e monohydrate, HSC^CF-^^O which melts at 30°C.  The formation of t h i s hydrate necessitates the use of  a dry box to handle the a c i d . on occasion proved u s e f u l .  The formation of the monohydrate has  When water i s generated i n a r e a c t i o n ,  the a c i d e f f e c t i v e l y removes the water from the r e a c t i o n . normal uses HS0 CF 3  3  For a l l 28  can be handled i n the same manner as HS0 F 3  F i n a l l y , a word about the naming of HS0 CF 3  3>  The o r i g i n a l  synthesis c a l l s the a c i d t r i f l u o r o m e t h a n e - s u l f o n i c a c i d .  From the  point of view of inorganic nomenclature an argument can be made  14. for trifluoromethylsulfuric acid. in the l i t e r a t u r e .  Various other  permutations e x i s t  There i s even a proposal that s a l t s of HSCLCF., Q V  J o  be c a l l e d " t r i f l a t s " f o r the sake of b r e v i t y .  In t h i s t h e s i s , however,  the a c i d w i l l be c a l l e d t r i f l u o r o m e t h a n e s u l f o n i c a c i d and d e r i v a t i v e s of i t trifluoromethanesulfonates.  The main reason f o r t h i s d e c i s i o n  i s to avoid confusion and promote c l a r i t y .  As f o r choosing the  organic name over the inorganic name no real reason e x i s t s but the terminology used i s that most common in the l i t e r a t u r e .  15. Experimental A.  Chemicals 1.  Reagents  Except f o r p e r o x y d i s u l f u r y l d i f l u o r i d e ,  RbCUSO^F)^] and cesium  trifluoromethanesulfonate a l l the reagents used i n the synthesis of the various iodine trifluoromethanesulfonates were e i t h e r a v a i l a b l e commercially^or else were trifluoromethanesulfonates^ where the synthesis i s the subject of t h i s t h e s i s , a.  Commercial i)  Elemental iodine was supplied by the Fisher S c i e n t i f i c Com-  pany (resublimed) and 99% pure. ii)  No f u r t h e r p u r i f i c a t i o n was undertaken.  Elemental f l u o r i n e , 98% pure, used i n the preparation of  S 0gF2 was obtained from A l l i e d Chemical Corporation, and passed through 2  a sodium f l u o r i d e , NaF, metal trap to remove hydrogen f l u o r i d e , HF. No attempt was made to remove other i m p u r i t i e s commonly present i n the  s u c n  ^2  a s  o  r  ^2  s  i  n  c  e  ^ e y do not enter i n t o the reaction  between S0* and F2. A high pressure Autoclave Engineering Valve and 3  Crosby high pressure gauge regulated the flow of F iii) House.  2  from the c y l i n d e r .  Elemental bromine, 99% pure, was supplied by B r i t i s h Drug  I t was stored over P 0 2  5  and KBr and used without  further  purification. iv)  Elemental c h l o r i n e , 99.5% pure, was supplied by Matheson  of Canada L t d . H S0 2  4  It was dried by passing the gas through two 96%  traps and f i n a l l y through a P^O^ tube.  remove 0 or N or other i m p u r i t i e s . 9  9  No attempt was made to  16.  v)  S u l f u r t r i o x i d e was purchased from Baker and Adamson,  A l l i e d Chemical C o r p o r a t i o n , as " S u l f a n " ( s t a b i l i z e d S0 ) and used 3  without p u r i f i c a t i o n . vi)  Iodine pentoxide was obtained from Fisher S c i e n t i f i c Com-  pany ( p u r i t y 99%).  However, based on the i n f r a r e d spectrum of the  coupound i t was HIgOg ?fe?7. and not 1^0^. any attempt to p u r i f y .vii)  It was used as such without  it.  Iodic A c i d , H I 0 , was obtained from B r i t i s h Drug House at 3  a p u r i t y of 97.5%.  Again i t was found to be Hl^Og -J-. I.  It was  used without p u r i f i c a t i o n . viii)  Potassium i o d i d e , 99% pure, was obtained from Fisher  S c i e n t i f i c Company and used without f u r t h e r p u r i f i c a t i o n . ix)  Rubidium i o d i d e , 99% pure, was obtained from A l f a Inorganics  L t d . and used without f u r t h e r p u r i f i c a t i o n . x)  Cesium c h l o r i d e , 99.9% pure, was obtained from B r i t i s h  Drug House and used without f u r t h e r p u r i f i c a t i o n . xi)  Trifluoromethanesulfonic a c i d , HSO^CF^, was obtained from  the Minnesota Mining and Manufacturing Company as "Fluorochemical A c i d " and the p u r i t y was not g i v e n .  I t was p u r i f i e d by d i s t i l l a t i o n  under reduced pressure. xii)  F l u o r o s u l f u r i c A c i d , HSO^F, ( t e c h n i c a l grade) was supplied  by A l l i e d Chemical Corp. and was p u r i f i e d by double d i s t i l l a t i o n under 2d  dry nitrogen at atmospheric pressure - ^ J . b.  Prepared i)  Peroxydisulfuryldifluoride,  6^2'  w a s  P P r e  a r e a  "  i n  500 g.  q u a n t i t i e s i n a modified version of a general method reported by  17. *' .  Shreeve and Cady  >'.  was mixed with dry N  2  A f t e r having passed through a NaF t r a p , F^ and S 0  3  (sulfan) in a s i l v e r ( I I )  c a t a l y t i c furnace reactor F i g . 2 . and the  $2®(f2  9  e n e r a t e d  w a s  fluoride  The reaction temperature was 180°C  condensed out at -78°C in dry i c e t r a p s .  Any unreacted S 0 was removed by e x t r a c t i o n with Oleum, concentrated 3  h^SO^ and l a t e r 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 to y i e l d pure 19 S^Q^2  as i n d i c a t e d by ii)  F N.M.R. and i n f r a r e d spectroscopy.  Rubidium t e t r a k i s - f l u o r o s u l f a t e i o d a t e ( I I I ) , R b [ I ( S 0 F ) ] 3  4  was synthesized from Rbl and S,,0gF i n analogy to the reported syn2  t h e s i s of the potassium s a l t by L u s t i g and Cady  An excess of  (<ft).  S 0 g F was d i s t i l l e d onto Rbl and a f t e r several hours the excess 2  2  S 0 g F was removed leaving the R b [ I ( S 0 F ) ] as a white s o l i d . 2  2  3  No  4  p u r i f i c a t i o n of the product was necessary.  The r e a c t i o n was followed  by weight. iii)  Cesium t r i f l u o r o m e t h a n e s u l f o n a t e , C s S 0 C F , was obtained 3  fromCsCl and HS0 CF . 3  3  3  An excess of HS0 CF was added to CsCl i n a two 3  part reactor and a f t e r several hours the excess a c i d was removed leaving the iv)  CsS0 CF behind. 3  3  The r e a c t i o n was followed by weight.  Iodine t r i s f l u o r o s u l f a t e I ( S 0 F ) 3  3  and S 0 g F by the method of Roberts and Cady 2  2  S 0 g F was d i s t i l l e d onto I 2  2  room temperature.  2  was synthesized from  I  2  An excess o f  and the mixture was allowed to warm to  Heat was evolved and a greenish l i q u i d was formed.  E v e n t u a l l y , a f t e r leaving the reaction overnight, the l i q u i d became l i g h t yellow i n d i c a t i n g a complete r e a c t i o n .  The excess S 0 g F was 2  2  removed i n vacuo and the product used without f u r t h e r p u r i f i c a t i o n . The r e a c t i o n was followed by weight.  18.  2. a.  Products  I o d i n e ( I I I ) and Iodine(I) Trifluoromethanesulfonates. i)  Iodine t r i s t r i f l u o r o m e t h a n e s u l f o n a t e I ( S 0 C F ) 3  3.78 mmol.) was suspended i n 29 g . of HS0 CF 3  Then 2.453 g. (12.38 mmol.) of $2®6^2. from a c a l i b r a t e d t r a p .  w a s  a c  3  I^  3  (0.958 g.  in a two part r e a c t o r .  3  ' ' ' by c  e c  v  a  c  u  u  m  distillation  The mixture was allowed to warm to room tem-  perature and shaken manually from time to time.  The colour was  i n i t i a l l y brown and then changed to blue and blue green.  A f t e r 20-30  minutes the colour had changed to a l i g h t yellow and a p r e c i p i t a t e had begun to form.  The v o l a t i l e products were removed in vacuo and  4.307 g. of I ( S 0 C F ) 3  ii)  3  was obtained.  3  An a l t e r n a t e route to I ( S 0 C F ) 3  3  v i a I(S0 F.) -  3  3  HS0 F was d i s t i l l e d onto 2.9654 g. of I ( S 0 F ) 3  3  3  1 2  grams of  i n a two part reactor  3  The reactor was evacuated and introduced i n t o the dry box where a p p r o x i mately 8 grams of HS0 CF was added. 3  immediately. I(S0 CF ) 3  3  iii)  3  3  A yellow p r e c i p i t a t e was formed  V o l a t i l e components were removed and 3.8279 g. of  were obtained. Iodine(I) trifTuoromethanesulfonate, I S 0 C F ; i n a t y p i c a l 3  preparation 0.982 g. (1.72 mmol.) of I ( S 0 C F ) 3  3  3  3  and .460 g. (1.80  mmol.) of l£> both f i n e l y ground, were combined i n a t h i c k walled pyrex glass tube.  A f t e r flame s e a l i n g the r e a c t i o n the tube containing  one atmosphere of dry nitrogen was completely immersed i n an o i l bath at 135 C. P  Both r e a c t a n t s melted to a viscous dark brown l i q u i d .  No appreciable q u a n t i t i e s of  vapour could be detected v i s u a l l y .  The temperature of the o i l bath was r a i s e d to 145°C and the r e a c t i o n l e f t i n i t f o r one hour.  A f t e r c o o l i n g slowly the product s o l i d i f i e d  19. to a black brown cake.  Attempts to perform the reaction at higher  temperatures r e s u l t e d in decomposition with the formation of and a c l e a r c o l o u r l e s s l i q u i d .  ^  The r e a c t o r was broken open in the  dry box and the contents transfered to a two part r e a c t o r .  To ensure  complete r e a c t i o n , the powder was melted at 130°-135°C and then allowed to anneal s l o w l y .  A l l v o l a t i l e s were removed by vacuum  d i s t i l l a t i o n and the product was stored i n the dry box. b.  A l k a l i metal t e t r a k i s trifluoromethanesulfonate i o d a t e ( I I I ) s a l t s , i)  K [ I ( S 0 C F ) ] ; KI (0.239 g.) 3  3  4  i n a two part r e a c t o r was  dissolved in 19 g. of HS0 CF and o x i d i z e d by .607 g. of S^OgF . 3  :  3  The mixture was treated i n the same way as described f o r i n section ( I I A 2 a i ) .  2  I(S0 CF ) 3  3  3  White to s l i g h t l y y e l l o w i s h c r y s t a l s began to  form only a f t e r the volume of the l i q u i d had been considerably decreased.  A s o l i d (1.170 g.)  ii)  i d e n t i f i e d as K [ I ( S 0 C F ) ] was obtained. 3  3  4  R b [ I ( S 0 C F ) ] ; R b [ I ( S 0 F ) ] (0.892 g.) was d i s s o l v e d i n 3  10 g. of HS0 CF . 3  3  4  3  4  A f t e r removal of a l l the v o l a t i l e s 1.071 g . of  3  R b [ I ( S 0 C F ) ] was obtained as a white s o l i d . 3  3  iii)  4  C s [ I ( S 0 C F ) ] ; CsS0 CF 3  2  4  3  (0.245 g.) was d i s s o l v e d i n 10.7 g .  3  of HS0 CF and 0.472 g. of I ( S 0 C F ) 3  3  3  3  3  was added.  A c l e a r yellow s o l u -  t i o n formed from which C s [ I ( S 0 C F ) ] c r y s t a l l i z e d out as a white s o l i d . 3  c.  3  4  Iodyl and Iodosyl trifluoromethanesulfonate I 0 S 0 C F 2  i)  3  3  and I0S0 CF  Iodyl t r i f l u o r o m e t h a n e s u l f o n a t e , I 0 S 0 C F ; HI 0g (1.2211 2  3  3  3  3  g.)  and 20 g . of HS0 CF were s t i r r e d together i n a two part pyrex r e a c t o r 3  3  with a magnetic s t i r r e r f o r two and a h a l f days.  The s o l i d appeared  to be cTiffetee&t but at no time was a l l s o l i d d i s s o l v e d .  Upon removal  3  20. of a l l l i q u i d by f i l t r a t i o n the white s o l i d product was d r i e d under vacuum. ii) and I  Iodosyl t r i f l u o r o m e t h a n e s u l f o n a t e , I 0 S 0 C F ; H I 0 3  3  3  (.6017 g.)  8  (.3050 g.) were combined with 20 g. of HS0 CF i n a two part  2  3  reactor containing a magnetic s t i r r e r .  3  The mixture was s t i r r e d f o r one  week and the l i q u i d removed by f i l t r a t i o n .  The s o l i d product, which  was contaminated with small amounts of iodine was washed with HS0^CF . 3  The yellow s o l i d I0S0 CF was f u r t h e r d r i e d i n vacuo r e 3  moving the f i n a l traces of d.  3  l^.  Dihalo iodine trifluoromethanesulfonate i)  I B r S 0 C F ; IS0 CF 2  3  3  (1.2447 g.) was placed i n an evacuated  3  two part reactor connected with a glass T to a storage vessel of at room temperature. 2 part r e a c t o r .  Bromine vapour was admitted to the evacuated  A r e a c t i o n between the B ^ and the IS0 CF 3  place and was followed by weight.  took  3  The f i n a l product IBr2S0 CF 3  3  (1.9305 g.) was c a r e f u l l y d r i e d i n vacuo to remove excess B r . 2  ii)  I C 1 S 0 C F ; IS0 CF 2  3  3  3  3  (0.2897 g.) was placed i n a one piece  glass reactor and with the reactor at -196°C (cooled i n l i q u i d n i t r o gen) approximately 10 mis of c h l o r i n e was added by vacuum t r a n s f e r . The r e a c t i o n mixture was kept at -78°C in a dry i c e t r i c h l o r o e t h y l e n e s l u s h bath.  P e r i o d i c a l l y the reactor was shaken to promote r e a c t i o n .  While the reactor was s t i l l at -78°C the excess c h l o r i n e was removed i n vacuo.  Upon warming to room temperature, the orange s o l i d obr  tained l i q u i f i e d and turned yellow decomposing i n t o iii)  (IC1 ) . 3  2  I S 0 C F ; a t t e m p t s to synthesize ^ S t ^ C f ^ were made i n 3  3  3  s t r i c t analogy to the successful synthesis of  I3SO3F  (34) and the  21.  synthesis of ISO^CF^ described in t h i s study. of I  2  Only incomplete uptake  could be accomplished at the high temperature M40°C needed to  maintain the reactants in the molten s t a t e .  B.  Apparatus 1.  Vacuum Lines  Standard high vacuum techniques were employed with a l l the compounds described because of t h e i r r e a c t i v i t y toward oxygen and water vapour.  In order to achieve and maintain the vacuum necessary a  Welch Duo-Seal pump Model 1400, was used, capable of maintaining a vacuum of .001 t o r r .  The pump was connected to the l i n e through a  l i q u i d nitrogen cold trap to prevent any v o l a t i l e m a t e r i a l s from being drawn through the pump. a.  Glass l i n e The main manifold of the glass l i n e was constructed of Pyrex  tubing 600 mm. long and 20 mm. i n diameter, sealed o f f at one end and connected to the cold trap and manometer by a Fischer and Porter 4 mm. glass and t e f l o n stopcock and a B19 ground glass cone and socket joint.  Four a d d i t i o n a l Fischer and Porter stopcocks served as i n l e t s  to the manifold f o r attaching reactors and other apparatus v i a B10 ground glass cone and socket j o i n t s .  Pressures in the manifold  were measured with a mercury manometer which was attached to the main l i n e by a Kontes stopcock and a B10 cone and socket j o i n t . b.  Monel Metal Line In the attempted preparation of B r ( S 0 . X F ~ ) - , where the reagent  22. BrF^ i s known to attack g l a s s , a monel metal l i n e was used.  This l i n e  i s a standard metal vacuum l i n e and has been previously described in the M.Sc. t h e s i s of Larry Levchuck 2.  ..  Metal Fluorine Line  For the preparation of $2®6^2 ^ s u i t a b l e f o r flow r e a c t i o n s .  w a s  n  e  c  e  s  s  a  r  v  to  u s e  a  system  The f l u o r i n e l i n e used consisted b a s i c a l l y  of a skeleton of copper tubing and Whitey, Hoke, and Autoclave Engineering v a l v e s .  The valves were supplied by Whitey Research Tool C o . ,  Oakland, C a l i f o r n i a ; Hoke I n c . , C r i s k i l l , New J e r s e y ; and Autoclave Engineering I n c . , E r i e , Pennsylvania r e s p e c t i v e l y .  Fluorine was i n -  troduced through a NaF trap which could be regenerated by heating e l e c t r i c a l l y to remove any HF which became absorbed in i t .  The  f l u o r i n e could then be mixed with dry nitrogen or used undiluted and led d i r e c t l y i n t o a c a t a l y t i c reactor furnace. furnace permitted the a d d i t i o n of SO^ gas.  Another i n l e t to the  This system i s shown  schematically in f i g u r e 2. 3.  Dry Atmosphere Box  A l l manipulation of s o l i d a i r s e n s i t i v e m a t e r i a l s and a l l additions of HSO-jCF^ were c a r r i e d out in a Vacuum Atmosphere Corporation "Dri Lab" Model No. HE-43-2, f i l l e d with p u r i f i e d dry n i t r o gen and equipped with "Dri T r a i n " Model No. HE-93B.  In order to  make q u a n t i t a t i v e additions in the dry box a M e t t l e r PI60 top loading balance was used. 4.  Reactors  a.  Two Part Glass Reactor  For the most part reactions were c a r r i e d out in a two part  Crosby  Pressure Guage  To F l o w m e t e r Copper i  Glass i  To F cylinder 2  To F l o w m e t e r !  5COml. Pyrex Flask  Reactor  Copper  Glass ^V7  (f)  Whitey V a l v e  r  - 0 - Hoke 4 1 3 V a l v e  B34  To S o d a - lime T r a p B 34  B34  •Fluorolube Oil T u b e  Autoclave Engineering Valves  B  C CO  Fig.  X  Apparatus- for the Preparation of S O F 2  s  2  24. pyrex glass r e a c t o r .  The reaction f l a s k was a 50 m l . round bottom  f l a s k with a B19 cone top.  The reactor top consisted of a Teflon  stem stopcock (Fischer and P o r t e r , or Kontes) j o i n i n g i n l i n e a B19 socket, to be f i t t e d to the f l a s k , and a BIO cone, f o r attachment to the glass vacuum l i n e . b.  One Part Glass Reactor. In the attempted synthesis of ICl^SO^CF^  /  ISO^CFg a one part pyrex glass reactor was used. a pyrex tube  a n c  j -j  purifying  n  This consisted of  20 mm diameter sealed at one end with a Teflon s t o p -  cock at the other.  In the attempt to prepare B r ( S 0 C F ) 3  3  3  a similar  reactor u t i l i z i n g a quartz reactor and a graded quartz glass seal was used. c.  Thick Walled Glass Tube Reactor In the preparation of IS0 CF 3  3  where I  2  and I ( S 0 C F ) 3  3  3  are  combined at 145°C high pressures were p o s s i b l e . For t h i s r e a c t i o n then a t h i c k - w a l l e d Pyrex tube of 20 mm outer diameter sealed at one end and with a c o n s t r i c t i o n near the other end which had a B19 cone on i t was used.  The two s o l i d s were introduced v i a glass  funnels whose stems protruded beyond the c o n s t r i c t i o n . was f i t t e d v i a the B19 cone, with a P 0 2  5  The reactor  drying tube to prevent the  entrance of moisture when the tube was sealed with a flame i n the a i r . d.  Two part Monel reactor As mentioned above, when B r F  apparatus had to be avoided.  3  was used as a reagent glass  When large q u a n t i t i e s of B r F  3  were  handled f o r long periods at elevated temperatures the quartz reactor  described above was not s u i t a b l e and a two part monel metal reactor was used.  A s u i t a b l e monel reactor consisted of a c y l i n d r i c a l metal  pot of about 100 m. capacity which was connected with s i x b o l t s to a l i d equipped with a Hoke valve (#431).  A vacuum t i g h t seal was  achieved with a t e f l o n r i n g inserted i n t o a groove between the pot and the l i d .  This reactor could be attached d i r e c t l y to the metal  l i n e using Swagelok connections. The  two  types of glass reactors described above are shown  in f i g u r e 3 and the metal reactor i n f i g u r e 4 . 5. a.  Miscellaneous  Vacuum F i l t r a t i o n Apparatus A pyrex d e v i c e , s i m i l a r to the one described by Shriver  (35),  designed to separate l i q u i d s from s o l i d s by f i l t r a t i o n under p a r t i a l vacuum was also used.  The apparatus consisted of a 25 mm, outer  diameter glass tube i n which a medium coarseness glass f r i t was set about one t h i r d from the bottom.  The top of the tube ended i n a  B19 socket f o r connecting a reaction f l a s k from a two part glass reactor and at the bottom was a B19 cone f o r attaching a 250 ml round bottom f l a s k with a B19 socket.  Below the glass f r i t a side arm  o u t l e t connected to a 4mm bore greased stopcock and a BIO cone. . This allowed attachment to the glass vacuum m a n i f o l d .  The o v e r a l l  length  of the apparatus without the f l a s k s i s 350 mm. b.  L u b r i c a t i n g grease A l l ground glass j o i n t s described i n the preceding sections  were l u b r i c a t e d with a low v o l a t i l i t y grease designed  to be i n e r t  TEFLON  STEM  STOPlCCK  TEFLON  B - I O G R O U N D GLASS CONE  8-10  THIN  STEM  GROUND GLASS  or THICK WALL  PYREX GLASS B-I9 GROUND GLASS . CONNECTION  FIGURE  3  TWO-PART  GLASS REACTOR  I  ONE  PIECE  GLASS  STOPCOCK  REACTOR  CONE  3  CVJ  Hoke  V a l v e ( N o 431)  Monel Metal  Tube  Eolts to S e c u r e L i d to B o t t o m V e s s e l  |^ Lid  n  .  .  C o n d e n s e r Inlet  |i fl  a:  Bottom C o n d e n s e r Inlet  Monel  F i g . 4\ Monel Metal 2 - P a r t  Metal R e a c t i o n Vessel ( 1 5 0 ml )  Reaction V e s s e l " ( Front V i e w )  to f l u o r o acids and to maintain leakproof connections under vacuum. The grease was supplied by Hooker Chemical Company, F a i r l a w n , New J e r s e y , as Fluorolube grease GR-90 d i s t r i b u t e d by Fisher S c i e n t i f i c Company, c.  Analyses A l l elemental analyses were performed by A l f r e d Bernhardt  M i c r o a n a l y t i c a l L a b o r a t o r i e s , Elbach, West Germany. C.  Spectrophotometers  1.  Infrared Spectrometer  Infrared spectrographs were recorded using a Perkin Elmer Model 457 Grating Infrared Spectrophotometer i n the range 4000-250 cm . - 1  Samples were genreally run neat between two s a l t windows.  Due to the high r e a c t i v i t y of a l l samples there was no s u i t a b l e m u l l i n g agent.  Because of the high r e a c t i v i t y of the samples the  windows were made from s i l v e r bromide, AgBr.  Even these were  sometimes attacked although only a f t e r prolonged exposure.  KP.S5  windows were severely attacked and both sodium c h l o r i d e and s i l v e r c h l o r i d e windows were of too l i m i t e d range t o use. ;  IB^SO^CF^ was  unreactive towards Cesium iodide and these windows were used. windows were supplied by Harshaw Chemicals.  All  Gaseous samples were con  tained i n a monel c e l l f i t t e d with a Whitey IKS^ valve and AgCl windows. 2.  Raman Spectrophotmeter  The Raman spectra of the compounds were measured with a Cary 81 spectrophotometer using a Spectrophysics Model 125 He-Ne l a s e r  source with an e x c i t i n g l i n e at 6328 A. were f i l l e d i n the drybox.  The pyrex sample tubes  The tubes were 5 mm outer diameter pyrex  glass with an o p t i c a l l y f l a t end.  The tube was about 120 mm long  and a f t e r f i l l i n g was sealed with a flame. 3. U.V.  V i s i b l e and U l t r a v i o l e t  Spectrophotometer  v i s i b l e spectra were recorded on a Cary 14 spectrometer.  The samples were contained i n 1 mm path length quartz c e l l s f i t t e d with a i r t i g h t t e f l o n stoppers. Instruments L t d . i n the dry box.  The c e l l s were obtained from ISC  A l l d i l u t i o n s and f i l l i n g of c e l l s were performed  30. Results and Discussion A.  Introduction  Compounds of p o s i t i v e l y p o l a r i z e d halogens with strong oxyacids as pointed out i n the i n t r o d u c t i o n have been known f o r many y e a r s .  The  number of compounds obtainable from any one a c i d i s found to be prop o r t i o n a l to the strength of the a c i d .  By f a r the l a r g e s t number of  compounds which have been synthesized are d e r i v a t i v e s of f l u o r o s u l f u r i c acid.  There are three main reasons f o r t h i s abundance: a.  F l u o r o s u l f u r i c i s one of the strongest oxyacids known.  b.  The peroxide of HSO^F, ^2^6^2'  1 S  a  s  *  r o n  9 o x i d i z i n g agent  and very s u i t a b l e as a s y n t h e t i c reagent. c.  Halogen f l u o r o s u l f a t e s u n l i k e perchlorate are very thermally  stable. A r e l a t i v e l y new a c i d , t r i f l u o r o m e t h a n e s u l f o n i c a c i d should be comparable i n a c i d strength (or protonating a b i l i t y ) to HSO^F. have been claims  There  that i t i s the strongest a c i d known.  I t became i n t e r e s t i n g , t h e r e f o r e , to see what halogen t r i f l uoromethanesulfonates might be synthesized.  The most common type  of c a t i o n i c compound formed generally by the l a r g e s t number o f oxyacids are the i o d i n e l l l compounds. f i r s t the synthesis of iodine CUT)  It seemed reasonable to attempt t r i s t r i fluoromethanesul f o n a t e ,  I(S0 CF )3. 3  3  B. 1.  Synthesis  I o d i n e ( I I I ) t r i s t r i f l u o r o m e t h a n e s u l f o n a t e , I(SO^CF^)^.  Iodine  33 trisfluorosulfate  , the pattern compound f o r I(SO^CF^)^ was o r i g i n a l l y  31. prepared with the peroxide, S^OgF^, which can be regarded as a 37 pseudo halogen  according t o : I  +  2  3(S0 F) 3  —^2I(S0 F)  2  3  in a simple and straightforward way. has been w r i t t e n as ( S 0 F ) 3  character.  The S 0 g F 2  (8)  3  2  i n the r e a c t i o n above  to i l l u s t r a t e more c l e a r l y i t s pseudohalogen  2  Unfortunately and somewhat s u r p r i s i n g l y , the analogous 25  peroxide S 0 g ( C F ) 2  3  2  had been found previously to be thermally unstable  Th us the analogous route to I ( S 0 C F ) 3  The f a c t that H S C F n  3  3  3  did not appear to be f e a s i b l e .  i s known to l i b e r a t e HCl from metal  3  17 23 chlorides such as NaCl , dimethyl t i n d i c h l o r i d e and titanium 25 tetrachloride  suggested that the replacement of c h l o r i n e i n IC1  mi ght be f e a s i b l e .  3  As excess of HS0 CF was added to f r e s h l y prepared 3  3  IC1^ but when the excess acid was removed a f t e r 72 hours the dark red product was i d e n t i f i e d by i t s Raman spectrum as IC1. that I C 1  3  It appears  undergoes decomposition which i s not unexpected f o r t h i s  compound and the method was u n s u c c e s s f u l . A s i m i l a r attempt involved the replacement of f l u o r o s u l f a t e with trifluoromethanesulfonate i n I ( S 0 F ) . 3  3  I n i t i a l l y the simple  reaction of I(SO^F)^ with excess HS0 CF was attempted a s : 3  I(S0 F) 3  I(S0 F) 3  3  +  3  3HS0 CF 3  3  3  HS0,CF, ^—^I(50 CF ) 3  3  3  + 3HS0 F 3  i s soluhble in HS0 F and i t was hoped that i t would a l s o be 3  s o l u - b l e HS0 CF . 3  3  When the reaction was attempted the f o l l o w i n g  observations were made.  The I(SO^F)^» a c l e a r viscous supercooled  (9)  .  32. l i q u i d at room temperature, turned i n t o a yellow s o l i d material upon contact with HSO3CF3. However, upon removal of the excess a c i d i n vacuo the weight of the s o l i d indicated l e s s than complete r e placement of SO3F by SO3CF3.  The gummy s t i c k y appearance of the  s o l i d also suggested an incomplete r e a c t i o n producing a mixture of I(S0 F) 3  3  and I ( S 0 C F ) . 3  3  3  Two useful conclusions may be drawn from t h i s experiment. F i r s t , S0 F groups may be replaced by $ 0 C F 3  3  3  groups in the iodine  tH  compound and second, the r e s u l t i n g products, in contrast to I ( S 0 F ) , 3  may be i n s o l u b l e i n the parent a c i d .  3  However, i t appears that the  formation of the s o l i d upon contact with HS0 CF occluded some of 3  3  the very viscous I(SO^F}^ preventing a complete replacement r e a c t i o n . In order to prevent t h i s o c c l u s i o n the synthesis of I ( S 0 F ) 3  3  in HS0 CF by method 2a!l (see experimental) was considered. 3  3  HSO.CFh  3 3 HS0 CF  +  6 H S 0  3  C F  +  3  3S  2°6 2 F  L  ^2I(S0 CF ) 3  3  " ^  3 ( s )  1  +  2 I ( S 0  3  F )  3(solv)  +  6 H S 0  3  C F  3 (10)  6HS0 F 3  A f t e r about 20-30 minutes at room temperature the colour of the s o l u t i o n undergoes changes from dark murky brown to pale c l e a r y e l l o w . The changes noted a r e :  dark brown to dark blue green to pale y e l l o w .  Some slowly decreasing amounts of s o l i d iodine are present in both the dark brown and dark blue green phases. has been consumed.  When the s o l u t i o n turns yellow a l l iodine  The yellow s o l i d product which i s formed appears e i t h e r  during the green phase or a f t e r the s o l u t i o n turns y e l l o w .  When the s o l i d  formation occurs in the c l e a r y e l l o w s o l u t i o n small n e e d l e l i k e c r y s t a l s  33. may be observed forming.  If i n s u f f i c i e n t peroxide i s used the f i n a l  s o l i d material i s tinged with blue green.  Whether the s o l i d forms  before or a f t e r the yellow phase appears seems to depend on whether the reaction mixture i s warmed to room temperature q u i c k l y or s l o w l y . The f i n a l stage i n d i c a t e d by the colour change from blue green to y e l l o w , appears to be exothermic. The colour changes observed deserve some comment.  Molecular  iodine i s only s l i g h t l y s o l u t b l e i n HSO^CF^ g i v i n g r i s e to f a i n t l y purple s o l u t i o n s .  The presence of an o x i d i z i n g agent w i l l ,  however,  produce brown coloured s o l u t i o n s i n i t i a l l y and large amounts of iodine w i l l go i n t o s o l u t i o n .  The colour i s due to polyiodine cations such  + + 38 as 1^ and I^ which have been previously i d e n t i f i e d in other strong protonic acids such as HSO^F and f^SO^. produce the blue I  2  +  cation.  The green colour observed i n t h i s reaction  may be due to mixtures of blue I the yellow 1(19)  species.  Further o x i d a t i o n should  2  with e i t h e r brown I3  (or 1^ ) or  Note the increase i n the formal o x i d a t i o n  state of iodine from 0 through +1/5 and +1/3 to +1/2.  The I  i s only e x i s t e n t in very strong acids i . e . HSO^F or H ^ O y superacid media i . e . HSO^F/SbF^.  2  +  cation  or i n some  The f i n a l yellow colour i s due to  the complete o x i d a t i o n of iodine(O) to i o d i n e ( J H ) and t h i s i s subs t a n t i a t e d by the f a i n t yellow tinge of the s o l i d product.  While  previously none of these polyiodine cations have been found in HSO^CF^ the colours observed here may serve as a f i r s t i n d i c a t i o n that they do e x i s t .  Further evidence obtained by recording the e l e c t r o n i c  spectra i s required and w i l l be presented in a l a t e r chapter.  34.  As a precaution i n the synthesis described above a large excess of $ £ ( ^ 2 should be avoided.  A mixture of $2(^2  and HSO^CF^  showed complete m i s c i b i l i t y and no apparent sign of r e a c t i o n . a f t e r about 30 minutes exothermic e v o l u t i o n  However,  of a v o l a t i l e compound, 25  l a t e r i d e n t i f i e d by i n f r a r e d spectroscopy as CF^SO^F  was noted.  This i n d i c a t e s the attack of the S-C bond in HSO^CF^ by The success of the synthesis of I ( S 0 C F ) 3  3  SgO^.  v i a the above  3  route may be due to the f a c t that o x i d a t i o n of iodine takes precedence over the attack of the S-C bond in the s o l v e n t .  Any a d d i t i o n a l side  r e a c t i o n s , perhaps w i t h the excess of $20gF2 normally used would r e s u l t i n such rather v o l a t i l e by products as HSO^F, CF^SO^F and S 0 3  None of these should i n t e r f e r e with the i s o l a t i o n of the product. Another method f o r s y n t h e s i z i n g I ( S 0 C F ) 3  developed.  3  3  was subsequently  The o r i g i n a l method even though very successful i s some-  what wasteful of HS0 CF 3  3  ($150 a l i t e r )  since a large (10-20 f o l d )  excess i s required and separation from the HSO^F formed during the r e a c t i o n would be extremely, d i f f i c u l t considering the s i m i l a r p h y s i c a l properties of the a c i d s . HS0 CF 3  3  We\therefore added a s l i g h t excess of  to a s o l u t i o n of I ( S 0 F ) 3  3  i n HS0 F. 3  I(S0 CF ) 3  3  3  was formed  immediately and could be i s o l a t e d as i n the f i r s t method. Iodine t r i s t r i f l u o r o m e t h a n e s u l f o n a t e , I ( S 0 C F ) 3  3  3  i s a pale  yellow s o l i d melting at +117-120°C and decomposing at approximately 170°C.  This i s a rather n o t i c e a b l e departure from other i o d i n e ( H J : )  compounds of strong oxyacids.  Iodine t r i s p e r c h l o r a t e decomposes 39 when warmed from -45°C to room temperature and iodine t r i s f l u o r o -  35.  s u l f a t e melts at +33.7°C at room temperature.  A s i m i l a r melting point i s found f o r iodine  tristrifluoroacetate. and I ( S 0 C F ) 3  3  3  is  and i s often found as a supercooled l i q u i d  In p a r t i c u l a r the d i f f e r e n c e between I ( S 0 F ) 3  3  intriguing.  The s o l u b i l i t y of I ( S 0 C F ) 3  3  3  i n both HS0 F and HS0 CF 3  3  s l i g h t and t h i s also i s q u i t e d i f f e r e n t from I ( S 0 F ) 3  soluble in the parent a c i d .  Where I ( S 0 F ) 3  3  i s s a i d to  3  3  is  which i s very disproportionate  upon heating according t o : I(S0 F) 3  -IS0 F  3  +  3  IF (S0 F) 3  3  +  2  3S0  (11)  3  thermal decomposition of I ( S 0 C F ) , occurs at 170°C i n vacuo and 3  3  accompanied by p a r t i a l s u b l i m a t i o n . CF S0 CF 3  3  3  Decomposition produces S 0 and 3  as v o l a t i l e s and a small amount of yellow residue containing  iodine i n the +3 o x i d a t i o n s t a t e and s u l f a t e .  The observed properties  of a high melting p o i n t , high thermal s t a b i l i t y and i n s o l u b i l i t y  in  the parent acid i n d i c a t e that I(SO^CF^)^ may be a polymer as has 33 been suggested f o r I ( S 0 F ) 3  .  3  A l l the d i f f e r e n c e s mentioned above,  however, i n d i c a t e a basic s t r u c t u r a l d i f f e r e n c e between I ( S 0 F ) 3  I(S0 CF ) 3  3  3 >  Hopefully the v i b r a t i o n a l spectrum w i l l allow  c l a r i f i c a t i o n of these d i f f e r e n c e s . is  and  3  further  Elemental a n a l y s i s of I ( S 0 C F ) 3  3  3  found in table 4 . Subsequent to t h i s synthesis of I ( S 0 C F ) 3  3  3  a report has appeared  41 of the synthesis I(0C0CF ) 3  by: 3  +  60° 3HS0 CF — 3  3  7 2  1 = r  I(S0 CF ) 3  3  3  +  3H0C0CF  3  (12)  36.  TABLE 4 Elemental a n a l y s i s and Melting (decomposition)  Compound  Calc'd  I(S0 CF )3 3  3  RbI(S0 CF ) 3  3  4  K KS0 CF ) 3  3  I S0 CF 3  3  2  3  I0 S0 CF 2  3  I0S0 CF 3  Calc'd  Found  22.10  22.21  16.76  16.79  29.78  29.64  15.69  15.92  15.86  16.07  28.19  28.07  M.P. 119°C 208-212°C d.  190-200°C d.  3  3  2  Found  4  3  *For I B r  F%  Calc'd  210-215°C d.  3  I Br S0 CF  S%  Found  4  Cs K S 0 C F ) 3  1%  Points  S0 CF 3  3  45.98  46.16  11.62  29.12  29.46  *  41.20  41.40  10.41  43.46  43.20  10.98  20.65  20.45  122°C  13.08  13.39  72-75°C d.  10.26  18.51  18.28  315-230°C d.  11.15  19.52  19.26  235-240°C d.  11.57)  Br% was c a l c u l a t e d rather than S%.calc . 36.67 found 36. 18  37.  Elemental a n a l y s i s of C and I i n d i c a t e the formation of I ( S 0 C F ) 3  3  3  but the reported decomposition point (190°-192°C) i s not in agreement with our f i n d i n g s .  As no f u r t h e r evidence was given i t i s not p o s s i b l e  to draw a conclusion at t h i s time. .  I(S0 CF )2 3  3  cation  +  Like many i o d i n e ( I I I ) d e r i v a t i v e s , e . g . IC1  3  and I ( S 0 F ) 3  the  3  new compound, I(SG" CF ) may act as an S0 CF ~ ion donor towards 3  3  3  3  3  strong Lewis acids and as an S0 CF ~ ion acceptor towards compounds 3  containing the S 0 C F 3  3  group.  3  Whereas the l a t t e r group i s well  sented, with a l k a l i metal s a l t s the most obvious case, no Lewis acid of the type E ( S 0 C F ) 3  3  n  repre-  well proven  was a v a i l a b l e to us.  42 Recently Yeats and Aubke  had found that SbFg and A s F may g  abstract the S0 F~ ion from f l u o r o s u l f a t e s such as CIC^SC^F,  It  3  seemed reasonable to attempt the S0 CF ~ a b s t r a c t i o n with SbFg. 3  However, the a d d i t i o n of SbF  5  3  to I ( S 0 C F ) 3  3  3  caused an immediate colour  change from yellow to deep b l u e , i n d i c a t i n g the formation of the ion^  &n ion which i s p e r f e c t l y s t a b l e i n SbFg.  This observation  best explained by assuming a d i s p r o p o r t i o n a t e of I ( S 0 C F ) . 3  3  is  As  3  a r e s u l t of t h i s f a i l u r e f u r t h e r studies i n t h i s system were not undertaken.  As i n the f l u o r o s u l f a t e system where S n ( S 0 F ) 43 3  to be an S0 F acceptor 3  4  proved  more success may be expected from Sn(S0" CF ) , 3  3  4  however, t h i s compound was synthesized only a f t e r t h i s study had been completed. .  A l k a l i metal t e t r a k i s (trifluoromethanesulfonato)  iodate(III) M[I(S0 CF ) ] 3  The s y n t h e s i s . o f several compounds containing the [ I ( S 0 C F ) ] ~ 3  3  4  3  4  38.  anion was s u c c e s s f u l .  This species should be s t a b i l i z e d best by the  heavier a l k a l i metal c a t i o n s ; K , Rb  and Cs .  Accordingly K[I(SO^CF^)^],  R b [ I ( S 0 C F ) ] , and Cs[I(SO^CF^)^] were prepared, each by a d i f f e r e n t 3  synthetic  3  4  route.  The synthesis of K [ I ( S 0 C F ) ] was c a r r i e d out according to 3  3  4  methodJtifoi: in the experimental s e c t i o n : HSO.CFKI + 2 S 0 F 2  g  + 4HS0 CF  2  3  J  3  » K[I ( S O g C F ^ ] + 4HS0 F  J  (13)  3  i n a manner s i m i l a r to the o r i g i n a l synthesis of I ( S 0 C F ) 3  3  3  equation 10.  Not unexpectedly the s a l t K [ I ( S 0 C F ) ] was q u i t e soluable in HS0 CF 3  3  4  3  and could only be i s o l a t e d by removal of the s o l v e n t .  No mixed  s a l t s were found as shown by the v i b r a t i o n a l s p e c t r a .  Whether the  r e s u l t i n g product was a mixture of KS0 CF and I ( S 0 C F ) 3  upon an a n a l y s i s of the s p e c t r a .  3  3  3  3  3  w i l l depend  However, the high melting point  210-215°C may serve as a preliminary i n d i c a t i o n of the p u r i t y of the compound. R b [ I ( S 0 C F ) ] was synthesized by the method 3  3  'i given in the  4  experimental section as: HSO-CF, R b [ I ( S 0 F ) ] + 4HS0 CF 3  4  3  3  J  J  > R b [ I ( S 0 C F ) ] + 4HS0 F 3  3  4  3  (14)  Again a complete conversion from the f l u o r o s u l f a t e to the t r i f l u o r o methanesulfonate was obtained. F i n a l l y , the synthesis of C s [ I ( S 0 C F ) ] was c a r r i e d out 3  3  4  according to the method given in sectioni$|)$iof the Experimental: HSO CF CsS0 CF 3  3  +  I(S0 CF ) 3  3  3  Cs[I(S0 CF ) ] 3  3  4  (15)  39.  A l l these methods are very straightforward and y i e l d high melting (190-215°C) pale yellow hygroscopic s o l i d s .  The composition  of R b [ I ( S 0 C F ) ] was confirmed by an elemental a n a l y s i s (given in 3  3  4  table 4) and the cesium and potassium s a l t s were checked by comparing t h e i r i n f r a r e d spectra with that of the rubidium s a l t .  Melting  points f o r a l l three compounds are l i s t e d in table 4. 4. Iodine monokistrifluoromethanesulfonate,  IS0 CF 3  3  The only previously known i o d i n e ( I ) compounds of oxyacids are a poorly characterized yellow n i t r a t e ^ which i s r e p o r t e d t o be stable only below room temperature, an i o d i n e ( I ) perchlorate  45?*"^ 'was o r i g i n a l l y  postulated as a reaction intermediate, but has never been i s o l a t e d i n substance, despite recent attempts  39  *" 34 and Iodine(I) fluorosulfate . 1  A  The l a t t e r compound has been produced from the i n t e r a c t i o n of a and Sfl^^  s t o i c h i o m e t r i c amount of vestigated.  and has been e x t e n s i v e l y in-?  The brown s o l i d product (m.p. 51.6°C) i s found to be  ex t e nsi ve l y d i s s o c i a t e d in strong protonic acids such as HS0 F 3  according t o : 5IS0 F 3  -21*  +  HS0 F) 3  3  + • 2S0 F"  (16)  3  34 to give blue green solutions the formation of I ( S 0 C F ) 3  3  3  . The observation of s i m i l a r colours by o x i d a t i o n of I  a similar dissociation in this acid. the synthesis of IS0 CF 3  3  2  in HS0 CF 3  3  in  indicate  The d i s s o c i a t i o n w i l l  preclude  i n HS0 CF . 3  3  In t h e i r study of the i o d i n e - f l u o r o s u l f a t e system, Chung and 40 Cady  have produced the phase diagram  f o r the  iodine-peroxydisulf-  40.  u r y l d i f l u o r i d e system ( f i g u r e 5 ) .  It was t h i s phase study which led  to the choice of a s y n t h e t i c route to ISO^CF^.  This phase diagram  shows, f i r s t of a l l , that ISO^F i s a real compound. \£  o  r  species g i v i n g r i s e to paramagnetism or the c h a r a c t e r i s t i c  blue colour was found in the melt. I(S0 F) 3  Secondly, no >  T h i r d l y , the t r a n s i t i o n s from  over ISO^F and ^SO^F to ^SO^F occur without a gap, which  3  implies that any compound can be converted into any other by a d d i t i o n of I  2  or S£0gF2.  s u l f a t e system.  Our method draws on the analogy to the f l u o r o -  Although we do not have the corresponding  S20g(CF )2, as mentioned e a r l i e r , by combining  peroxide,  and I ^ O ^ C F . ^  3  in the c o r r e c t mole r a t i o i n the melt a l l the compounds r i c h e r i n iodine than I ( S 0 C F ) 3  3  3  such as I S 0 C F , 3  should, i f they e x i s t , be formed.  3  I S0 CF 3  3  3  and I ( S 0 C F ) 7  3  3  The synthesis of ISO^CF^ was'i  s u c c e s s f u l l y c a r r i e d out by the method given i n the experimental sectionl'<$"according t o : 140°C h(l)  +  l{S  W3(i)  -  3 I S 0  3  C F  3  ( 1 7 )  The high reaction temperature was necessary to obtain both reactants i n the molten s t a t e .  Higher temperatures ( e . g . 170°C)  r e s u l t e d i n thermal decomposition.  I n i t i a l l y there was noticeable  purple iodine vapour above the brown black melt. reaction proceeded t h i s vapour was consumed.  However, as the  Because the iodine and  the i o d i n e ( I I I ) trifluoromethanesulfonate were combined i n s t o i c h i o metric proportions elemental a n a l y s i s i s not conclusive proof of a new compound.  The analysis i s reported in table 4 .  The high  41. '  Figure 5  Melting point i°Cl  o  42. melting point 122°C and more c o n c l u s i v e l y the v i b r a t i o n a l do i n d i c a t e that the compound i s I S 0 C F . 3  i s indeed IS0 CF 3  IS0 CF 3  Proof that the product  3  rests on the a n a l y s i s of the i n f r a r e d spectrum.  3  i s a dark brown hygroscopic s o l i d .  3  i s 121-122°C and i t i s thermally s t a b l e to pressure. (CF ) S0 3  2  .  3  spectrum  Its melting point  170°C under atmospheric  At i t s decomposition point the formation of I S 0 » and 2 >  3  i s noted suggesting the decomposition r e a c t i o n :  2IS0 CF 3  -  3  I  2  +  S0  +  3  (CF ) S0 3  2  (18)  3  I t should be noted as evidence that ISO^CF^ i s a true compound and not a mixture, that no iodine vapour i s observed at the melting point or below, even under vacuum. The dark brown colour of ISO^CF^ i s i n good agreement with the colour of IS0 F and also IC1 and does not agree with the yellow 3  colour found f o r i o d i n e ( I ) n i t r a t e .  The melting point of  (+122°C) i s much higher than that of the f l u o r o s u l f a t e . very s i m i l a r to the s i t u a t i o n f o r I(SO^CF^)^ 5.  Polyhalogen and  Interhalogen  a n c  IS0 CF 3  3  This i s  l I(SO^F)^•  trifluoromethanesulfonates I X S 0 C F 2  3  The phase diagram of the i o d i n e - p e r o x y d i s u l f u r y l d i f l u o r i d e  3  X=I,Br,Cl system  also i n d i c a t e s the existence of iodine r i c h f l u o r o s u l f a t e s of the composition ^SO^F and probably IySO-^F.  Even though some decomposition  34 to I  2  and I S F seems to occur I^SO^F n  3  was i s o l a t e d and characterized  but 1^SO^F which seemingly undergoes more extensive decomposition could not be i s o l a t e d .  43.  In an attempt to extend the f l u o r o s u l f a t e analogy to t r i fluoromethanesulfonates attempts were made to synthesize I^SO^CF^ according t o : ~140°C 2U)  l  +  I S 0  3  3(i)  C F  ( 1 9 )  However, despite repeated attempts only incomplete uptake If  of I^ from the gas phase occured.  Unlike the s i m i l a r synthesis of  ISOgCF^, the gas phase remained coloured during the r e a c t i o n .  All  that was obtained upon removal of the v o l a t i l e s under vacuum was a b l a c k , tsnhomogeneous, t a r l i k e substance containing small amounts of crystalline iodine.  The temperature needed f o r reaction necessitated  by the high melting point of I S 0 C F 3  decomposition temperature of the I  3  +  3  i s probably higher than the group i n a hypothetical  I S0 CF . 3  3  3  One should keep i n mind that the conversion of IS0 F (m.p. 50.2°C) 3  to I3SO.JF may be performed at  +65°C whereas i n t h i s r e a c t i o n the  140°C necessary i s already 70°C above the decomposition point of the I  3  +  cation i n I3SO.3F  3 4  .  Two f l u o r o s u l f a t e s , s i m i l a r to I S 0 F , that i s 3  3  IBr S0 F 2  3  and ICl^SO^jF ^ are both obtainable by s t r a i g h t a d d i t i o n a s : X  2  +  IS0 F  -IX S0 F  3  2  3  where X = Cl or Br  An attempt was made to prepare the corresponding S 0 C F 3  by combining s o l i d I S 0 C F 3  or s i i g h t l y below.  3  3  compounds  with the halogens at room temperature  (20)  44.  Chlorine gas was condensed onto ISO^CF^ at low temperatures, around 0°C, and was absorbed immediately.  The r e s u l t i n g orange sol i d «"«  warmed to room temperature where i t became l i q u i d and t h e ^ s o l i d i f i e d again to a yellow s o l i d .  The Raman spectrum of the yellow s o l i d  gave strong evidence f o r a mixture of ( I C 1 ) 3  ^  2  mixed with  I(S0 CF ) , 3  3  3  suggesting the f o l l o w i n g rearrangement: 3IC1 S0 CF 2  3  -(IC1 )  3  3  +  2  I(S0 CF ) 3  3  (21)  3  A l l attempts to prevent t h i s rearrangement and to i s o l a t e the o r i g i n a l orange compound at low temperatures were u n s u c c e s s f u l . Even i n samples produced at low temperatures the Raman l i n e s due to (IC1 ) 3  2  are found. Bromine vapour and I S 0 C F 3  stable at room temperature. with s o l i d IS0 CF 3  IBr S0 CF 2  3  3  3  at 0°C.  In a d d i t i o n I B r  a mixture of IBr and B r ment r e a c t i o n . 3  It would seem that the synthesis of  A m e l t , where rearrangements are achieved more teaalily  i s never formed.  3  Bromine vapour was allowed to react  i s p o s s i b l e because the r e a c t i o n occurs at 0°C i n the  solid state.  IS0 CF  reacted to give a product which i s  3  2  3  i s apparently nonexistent so that  are the probable products of a rearrange-  When l i q u i d bromine was allowed to react with s o l i d  at room temperature the product was a black s t i c k y s o l i d  which was l i g h t e r than expected f o r I B r S 0 C F . 2  3  The loss in weight  3  could be due to l o s s of bromine in the rearrangement according t o : •  3IBr S0 CF 2  3  3  *2IBr+2Br  2  +  I(S0 CF ) 3  3  3  (22)  45.  IB^SO-jCF^ i s a dark red brown hygroscopic s o l i d which melts at 72-75°C with p a r t i a l decomposition.  The s o l i d has a s l i g h t  tendency to decompose and become " s t i c k y " i f i t i s not pure; i f formation of IBr^SO^CF^  i s incomplete.  i.e.  The r e s u l t s of elemental  a n a l y s i s are shown i n table 4 and the v i b r a t i o n a l spectra w i l l be discussed l a t e r . IBr^SO^CF^ i s one of a very l i m i t e d group of I B r The only other  examples known are IB^SC^F  and  2  derivatives.  IB^Sb^ii  IB^SO^F was synthesized i n the manner mentioned above and IBr Sb F-|.| 2  2  was obtained by r e a c t i n g IB^SO^F with SbF^ according t o : IBr S0 F 2  3  +  3SbF  ••IB^Sb^  5  +  SbF^F  (23)  It appears that a d u p l i c a t i o n of the halogen-ISO^F reactions i s successful only f o r IB^SO-jCF^.  However, i t  addition should  be possible to form these compounds i n s o l u t i o n , provided a s u i t a b l e solvent can be found.  HS0 CF was studied as a possible solvent 3  3  and u l t r a v i o l e t and v i s i b l e spectra were taken on s o l u t i o n s of halogen X  2  and ISO^CF^ and compared with spectra of the corresponding  I X S 0 F compounds i n HSO^F. 2  3  ISO^CF^ alone i n HSO^CF^ gave a spectrum a t t r i b u t a b l e to  I . 2  +  48  The spectrum i s very s i m i l a r to that of IS0 F in HS0 F 3  3  which has  also been assigned to I and the p o s i t i o n s of the absorption maxima ... 49 + are s i m i l a r to those found by Kemmit et a l . for s o l u t i o n s of I 2  +  2  in SbFg.  By comparing the e x t i n c t i o n c o e f f i c i e n t s in each of these  46.  cases ,see table 5 a , i t can be seen that although they vary considerably i n magnitude, they are always in the same r e l a t i v e proportions. a b i l i t y of HS0 CF to support I 3  3  2  The  i n s o l u t i o n i s thus demonstrated  +  and the previous a t t r i b u t i o n of the blue-green colour formed during the synthesis of I ( S 0 C F ) 3  3  The existence of I X  as being due to I  3  2  (X = I,  +  2  is further substantiated.  +  Br, or C l ) i n HS0 CF was pos3  3  50 t u l a t e d , based on a study by Senior and Grover  demonstrating the  existence of these species in 100% s u l f u r i c a c i d and t h e i r existence 39 in  HSO^JF,  IBr S0 Cf 2  3  3  Solutions  of I  2  were i n v e s t i g a t e d .  tions  and ISO-jCF^; C l  and I S 0 C F ; as well as  2  3  3  The e l e c t r o n i c spectra of these s o l u -  are i d e n t i c a l to spectra of s o l u t i o n s of  IX S0 F 2  3  + fi  in HS0 F which have been shown to have been due to the species 3  IX  2  Having obtained the solvated cations as desired in s o l u t i o n the i s o l a t i o n of the compounds was attempted. I S0 CF 3  3  3  isolated.  was p a r t i c u l a r l y h o p e f u l .  The formation of  However, no s t a b l e compound was  Upon removal of HS0 CF under vacuum a l l that remained 3  3  were inhomogeneous t a r l i k e m a t e r i a l s while the v o l a t i l e products contained some molecular i o d i n e . 6.  Iodine-Oxygen Trifluoromethanesulfonates Some of the e a r l i e s t known compounds of p o s i t i v e l y p o l a r i z e d 13 iodine are the iodine oxygen d e r i v a t i v e s of oxyacids  .  Two types  of compound are encountered, the 1 0 - d e r i v a t i v e s , named i n analogy to NO compounds,  iodosyl compounds and the I 0  iodyl compounds.  The former ones were also regarded as " b a s i c " s a l t s  2  derivatives  labelled  of t r i v a l e n t oxyacid d e r i v a t i v e s suggesting, at l e a s t f o r m a l l y , the  46a.  Table 5a E x t i n c t i o n C o e f f i c i e n t s f o r it,  465  400  2368  836  815  IS0 F i n HS0 F  2186  580  630  I  2  i n oleum  1850  460  490  I  2  in  884  326  301  I  0  in SbF  1410  462  504  ylunax. (my) for  IS CF n  3  3  638  sample IS0 CF 3  3  Einax. (per  i n HS0 CF 3  3  3  IF  5  c  3  1^)  47..  existence of a base I ( 0 H ) , incomplete s a l t formation, and dehydration: 3  I(0H)  +  3  HY  -IOY  +  2H 0  (24)  2  It became i n t e r e s t i n g to extend t h i s study to SO^CF^ d e r i v a t i v e s  of  these two types. Iodyl trifluoromethanesulfaonate  I0 S0 CF 2  3  3  51 Iodyl s a l t s are known f o r some oxyacids i n c l u d i n g HSO^F Again where the S0 F compound had been obtained v i a : 3  I 0 2  +  5  S 0 F 2  6  *•  2  2I0 S0 F 2  (25)  3  Because of the u n a v a i l a b i l i t y of the peroxide an a l t e r n a t e route had to be devised.  The synthesis of I 0 S 0 C F 2  3  was c a r r i e d out as described  3  i n s e c t i o n - ^ ' : of the experimental a s : HI 0 3  +  g  3HS0 CF 3  -3I0 S0 CF  3  2  3  +  3  2H 0  (26)  2  The s t a r t i n g m a t e r i a l , H I 0 g , was at f i r s t thought to be iodine 3  pentoxide, I ^ 5 ' 2  anc  *  i n  ^  a c t  1 S  s  o  ^  a s  s u c n  -  However, when the  p u r i t y was checked by i n f r a r e d spectroscopy i t was found to be almost e n t i r e l y HI 0g. 3  This f a c t i s e x t e n s i v e l y discussed by S e l t e  29 and Kjekshus  who found most commercial samples of l 0 g and HI0 2  were contaminated with H I 0 g , or i n the case o f 3  even with  3  HIO^.  Because both the s t a r t i n g material and the product are white s o l i d s i t was d i f f i c u l t to judge whether a r e a c t i o n was complete or not. Therefore,  s t i r r i n g f o r more than 72 hours was found necessary to en-  sure complete r e a c t i o n .  48.  i s a white hygroscopic sol i d which decomposes between  IC^SO-JCF-J  310-320°C with purple iodine vapour r e l e a s e d . i s not unexpected f o r an iodyl compound.  The high melting point  Elemental a n a l y s i s given in  table 4 i n d i c a t e s that the compound i s indeed IO^SO^CF^.  The i n f r a r e d ,  and more c o n c l u s i v e l y , the Raman spectrum confirms t h i s and w i l l be discussed l a t e r . The p r i n c i p l e reason why conversion i s so r e a d i l y accomplished can be seen i n the f a c t that HSO^CF may act as a dehydrating agent. The water which i s formed during the synthesis immediately reacts with the HSOgCF-j, present i n a large excess, to form the s t a b l e mono27 hydrate  .  In a d d i t i o n , u n l i k e the S-F bond i n most f l u o r o s u l f a t e s  the S-C bond i n Su^CF-j compound appears to be r e s i s t a n t to  hydrolytic  attack. b. Iodosyl t r i f l u o r o m e t h a n e s u l f o n a t e , I0S0 CF 3  3  A m o d i f i c a t i o n of the synthesis of iodyl compounds suggested 52 by Masson and Argument methanesulfonate. HI 0g and I 3  2  afforded a route to the iodosyl  trifluoro-  The synthesis of I0S0 CF was c a r r i e d out using 3  3  in HS0 CF according to the method described in section 3  3  ~ZCf' of the experimental v i a : HIgOg + I I0S0 CF 3  3  2  + 5HS0 CF 3  3  HSCLCF. ^-^5I0S0 CF 3  3  + 3H 0  (27)  2  i s a yellow hygroscopic s o l i d which decomposes between 235  and 240°C.  The product was i d e n t i f i e d by elemental a n a l y s i s  4) as I 0 S 0 C F . 3  3  (table  V i b r a t i o n a l a n a l y s i s discussed l a t e r confirmed t h i s .  49.  An unsuccessful attempt was made to synthesize IOSO^CF^ by c o n t r o l l e d hydrolysis of I ( S 0 C F ) 3  3  in suspension in HSO^CF^ according  3  to: I(S0 CF ) 3  3  +  3  H0 2  HSCLCF. — i * . I0S0 CF 3  + 2HS0 CF  3  3  (28)  3  However, the a d d i t i o n of t r a c e amounts of water to I ( S 0 C F ) 3  3  results  3  r  instantaneously i n the occurence of the f a m i l i a r blue-green colour of I . 2  This i n d i c a t e s a d i s p r o p o r t i o n a t e or redox r e a c t i o n rather  +  than a s t r a i g h t f o r w a r d s o l v o l y s i s . For any previously synthesized iodine t r i f l u o r o m e t h a n e sulfonate a f l u o r o s u l f a t e analogue was known.  However, i n the case  of I 0 S 0 C F , no such analogue had been prepared. 3  The formation of 34  3  I0S0 F had been mentioned only b r i e f l y in the l i t e r a t u r e 3  as a pro-  duct of the h y d r o l y s i s of I ( S 0 F ) according t o : I(S0 F) + H0 -I0S0 F + 2HS0 F 3  3  3  3  2  3  The r e a c t i o n i s accompanied by a blue colour ( I ) 2  d i s p r o p o r t i o n a t e reaction.  (29)  3  +  suggesting a  The s o l i d product, however, was found  to contain s u b s t a n t i a l amounts of pentavalent i o d i n e , suggesting the claim of I0S0 F may be erroneous.  I t i s d i f f i c u l t to assess the c l a i m  3  as no a n a l y s i s i s reported. 53 Subsequent to t h i s work I0S0 F was prepared 3  analogous to that used f o r I 0 S 0 C F . 3  I0C0 CF 2  3  and ( I 0 ) P 0 F 2  2  2  failed.  3  by a method  Attempts "to form I 0 S 0 C H , 3  3  During the synthesis of I0S0 CF 3  the f a m i l i a r colour change sequence from brown to blue green to  3  50. yellow  was observed.  A s i m i l a r change was observed f o r the formation  of the f l u o r o s u l f a t e .  In the three unsuccessful cases the s o l u t i o n s  were at a l l times f a i n t l y tinged with r e d , i n d i c a t i n g iodine i n the 0 o x i d a t i o n s t a t e . This would, seem to suggest t h a t a p o s s i b l e p r e r e q u i s i t e f o r the formation of iodosyl compounds by t h i s method i s the c a p a b i l i t y of the a c i d to s t a b i l i z e I mediates in the o x i d a t i o n of 1(0)  to  3  +  (or I^ )  and  +  I(III).  as i n t e r -  The acids H P 0 F , 2  2  HSOgCHg and HC0 CF are weaker protonic acids than e i t h e r h^SO^, 2  3  h^SeO^, HSOgCFg and HSOgF, incapable of s t a b i l i z i n g even the l e a s t e l e c t r o p h i l i c of the p o l y i o d i n e cations I . 3  confirmed by experiment.  This point could be  +  A d d i t i o n of I3SO3F to e i t h e r HP0 F 2  2  or 55  HC0 CFg r e s u l t e d in the instantaneous formation of molecular iodine 2  7.  .  Bromine t r i s t r i f l u o r o m e t h a n e s u l f o n a t e A f t e r the f i e l d of iodine trifluoromethanesulfonates had been e x t e n s i v e l y i n v e s t i g a t e d attempts were made to form other halogen trifluoromethanesulfonates.  Observing t a b l e 3 in the i n t r o d u c t i o n  i t can be seen that f o r the f l u o r o s u l f a t e group the f o l l o w i n g compounds e x i s t .  BrtSOgFjg, BrSOgF and B r S O g F ^ " . W e therefore attempted  the synthesis of Br(S0gCF,j)g as an entry i n t o t h i s a r e a .  Complexation  hopefully would lead to B r ( S 0 C F ) ~ and reduction to BrSO^CF^. 3  3  4  The f i r s t attempt to form the B r ( S 0 C F ) 3  synthesis of I ( S 0 C F ) using B r 3  3  3  2  3  3  i n place of L,.  the r e s u l t s were inconclusive and alarming.  was to f o l l o w the Unfortunately  Upon warming, the mixture  of S 0 g F , B r , and HS0 CF detonated s h a t t e r i n g the r e a c t i o n vessel 2  2  2  3  3  51.  and thus d e t e r r i n g any f u r t h e r attempts v i a t h i s route. The a d d i t i o n of HS0 CF 3  to B r ( S 0 F )  3  3  which at f i r s t looked promising.  3  gave a red-brown s o l u t i o n  However removal of the solvent  d i d not y i e l d the expected product.  A brown v o l a t i l e m a t e r i a l ,  comparable i n v o l a t i l i t y to HS0 CF was obtained and i t was impossible 3  3  to e f f e c t a complete separation of the two. An a l t e r n a t e route was sought by the r e a c t i o n of B r F  3  and  HS0 CF as f o l l o w s : 3  3  BrF  3  +  3HS0 CF 3  *- Br(SG" CF ) + 3HF  3  3  3  (30)  3  The reaction was c a r r i e d out on a monel metal vacuum l i n e i n a quartz reactor.  Upon warming the c l e a r l i q u i d formed detonated with no  v i s i b l e sign of decomposition. abandoned.  At t h i s point the i n v e s t i g a t i o n was  Attempts to s o l v o l y s e B r F  3  i n HS0 CF 3  3  in a monel  reactor again only y i e l d e d v o l a t i l e m a t e r i a l s and no separation was attempted. C a t i o n i c bromine oxygen compounds are a l s o more unstable than the corresponding iodine compounds. prepared the compound K I 0 ( 0 C 0 C F ) 2  3  2  Naumann et a l .  by r e a c t i n g KI0 with 3  have (CF C0) 0 3  2  but attempts to prepare t h i s bromine analogue r e s u l t e d only i n an  m explosion.  H.A. C a r t e r ' s  attempts to prepare Bromine-oxygen  compounds of f l u o r o s u l f u r i c a c i d also met with f a i l u r e .  There s t i l l  may be a p o s s i b i l i t y of forming some bromine t r i f l u o r o m e t h a n e s u l f o n a t e s ^ however, the f i e l d should not prove to be as extensive as that of iodine trifluoromethanesulfonates.  C.  Vibrational  1.  General  Spectroscopy  Introduction  The main i n t e r e s t i n the v i b r a t i o n a l spectra of iodine t r i fluoromethanesulfonates i s centered on the SO^CF^ group, and even more narrowly on the S-0 v i b r a t i o n a l modes, because bonding of the SO^CF^ group to iodine or any other c e n t r a l atom w i l l most l i k e l y occur through the oxygen of the SO3 group.  In a general way the SO^CF^  group can be considered as SO^X with X = CF^.  An SO^X group can be  e i t h e r i o n i c , i . e . i n compounds of the type M^SO^X where K or N0 or c o v a l e n t l y bonded. +  =  In a l l of the c a t i o n i c halogen com-  pounds, the SO-jX w i l l probably be covalent due to the r e l a t i v e l y large e l e c t r o n e g a t i v i t y of i o d i n e . The highest symmetry f o r the SOgX" ion i s Cy.  If the ion  i s bonded c o v a l e n t l y through one oxygen, monodentate.or two oxygen, *\  bidentate^then the symmetry w i l l be reduced to C .  What t h i s w i l l  mean i n terms of the v i b r a t i o n a l freauencies i s summarized i n the c o r r e l a t i o n diagram o f SO^X i n f i g u r e  6.  When the SO^X group has C^v symmetry there are 6 normal v i b r a t i o n a l modes.  These are three A-j modes, one symmetric SO^  s t r e t c h , one SX s t r e t c h and one SO^ bend, and three degenerate E modes, one asymmetric SO^ s t r e t c h , one asymmetric SO^ bend and one rocking mode.  I f the SO^X group acts as a monodentate or bidentate  ligand then the reduction of symmetry to C r e s u l t s in the s p l i t t i n g s of the degenerate E modes and a l l 9 fundamental v i b r a t i o n s are observed.  FiyreL  Correlation Diagram for the  a)  s o  3  x 2 covalen\-monodentate C  *~  •' tonic C3V symmetry:  '  :  "E  A,  (J.R)' (409.)  <( l . R ) (786 )  v  V  . E' t  vSO s :.» ( I. R ) ,(1082)  type b) and c)  (l.R)  s o  »  a 3 (l.R) (592 )  ( 5 6 6 ) ..  j  A'  A"  .A"  (l.R)  ?  A'  A  Cl.R)  (l.R)  u  A' Cl.R.)  E = doubly  :1 = , i n f r a r e d a c t i v e  .R = , R a m a n ' a c t i v e s  • ^9  A = .nondegenerate  a = antisymmetric  '  E s so,  (l.R)  H  5  ^6  ^2  A*  *s  (I.R) (I287) i.  r  v  3  A,  v SO, a 3  • T  T-bidentate  i  A, .  S rock  vibration'for K S Q F in c m  *soX  c)  s  1  type a)  3  - oso  b)  group-  S0 X  A' Cl.R)  A" (l.R)  degenerate  = symmetric  us  54. In the SO^ s t r e t c h i n g region there i s a change from two s t r e t c h i n g modes to t h r e e .  The E mode i s s p l i t i n t o an A' and A" mode.  the bending region a s i m i l a r s p l i t t i n g i s observed. mode i s also s p l i t in the same manner.  In  The rocking  To complete the c i r c l e ,  i f the SOgX group i s t r i d e n t a t e , i . e . each oxygen i s bonded^then the symmetry i s once more C^v. This i s the general case f o r SO^X. SO^CF-j i s somewhat more complicated.  The p a r t i c u l a r case of  Assuming the CF  i $ t h e anion maintains the C^v symmetry, can be l o c a l i z e d C^  v  3  group, which  considered to have  symmetry in the covalent s i t u a t i o n where the SO^  symmetry i s reduced^then there are another 5 fundamentals to be expected.  And, i f the symmetry of the CF^ group i s reduced there woul  be another three bands in a d d i t i o n .  This i s shown i n the c o r r e l a t i o n  diagram f o r S 0 C F shown i n f i g u r e 7>. 3  3  As has been mentioned e a r l i e r , v i b r a t i o n a l studies of the SO^CF anion, i n c l u d i n g normal coordinate analyses and valence force f i e l d 20 21 c a l c u l a t i o n s have been reported by two groups  '  .  These two studies  do not agree on the assignment of the s p e c t r a .  The major d i f f i c u l t y  i n assigning the bands i s that the S 0 and CF  stretching vibrations  3  3  are of i d e n t i c a l symmetries f o r the ion (E and A-|) and unfortunately occur i n the same region of the spectrum.  Considerable mixing  the frequencies occurs r e s u l t i n g in a very complex spectrum. 21 purpose of t h i s d i s c u s s i o n the assignment of Burger et a l . The reason f o r t h i s i s that the S 0 and CF 3  3  of For the  i s used.  bands are assigned by  comparing the bands observed with bands assigned previously f o r other  FIGURE 7 Normal Vibrations of SO^CF^ groups with C^  Description  v CF &  C F  2  v  .  6 FCS v CS  6 S0  2  v  9  3 10  4  11  2  6 C-S-0 t o r s i o n C-S  ?  8 v  v 3  Symmetry  2  v,  3  v S0  A  v  12  5  * v  c  *This band i s i n a c t i v e i n both i n f r a r e d and Raman.  56.  compounds containing only S 0 and CF 3  groups.  3  A l s o , the assignments 54  are i n accord with trends observed i n other sulfonates  .  The assignment of spectra f o r c o v a l e n t , e i t h e r mono, b i , or t r i d e n t a t e groups should not be q u i t e as d i f f i c u l t as the because the l o c a l symmetry f o r the S e l i m i n a t i n g extensive mixing.  n  3  part of the molecule i s reduced,  Complications may a r i s e when there i s  more than one type of SO^CF^ group present. bands, which often c o i n c i d e . band contours.  i o n i c case,  This r e s u l t s in more  This leads to rather unresolved broad  When attempting an assignment of the compounds syn-  thesized i n t h i s thesis considerable help can be derived from the f a c t that examples of each coordination type f o r the SO^CF^ group may be found i n the l i t e r a t u r e .  Monodentate SO^CF^ groups are found in  ( C F ^ S O g whose i n f r a r e d spectrum has been reported by N o f t l e and Cady  i n FXeS0 CF  3  3  3  3 0  and i n (CH ) GeS0 CF 3  3  3  .  3  Bidentate bridging CA  S0 CF 3  3  i s found f o r organotin(IV) d e r i v a t i v e s  (CH ) Sn(S0 CF ) 3  2  3  3  ^  2  (CH ) SnS0 CF 3  3  3  and  3  where s t r u c t u r a l proposals are based on  ^Sn  Mossbauer spectra and the X-ray d i f f r a c t i o n study of the analogous t i n compound  (CH ) Sn(S0 F) 3  2  3  2  5 7  .  posed f o r the compound.TiCI S0 CF 3  3  A t r i d e n t a t e group has been pro2? 3  .  It may a l s o be noted that the spectrum of any of these S 0 C F 3  3  compounds i s quite s i m i l a r to the spectra of the analogous S0 F 3  compound.  The S 0 frequencies f o r the S 0 C F 3  3  3  compounds are s l i g h t l y  lower than f o r the corresponding f l u o r o s u l f a t e s .  This i s in accord  with the e l e c t r o n e g a t i v i t y arguments and a l s o the underlying bonding concept, that of d^-pir i n t e r a c t i o n based on the model discussed by  57.  Cruickshank  .  This trend i s i l l u s t r a t e d i n table 5 where a comparison  of ( C H ) S n ( S 0 F ) 2  5  2  3  2  and ( C H ) S n ( S 0 C F ) 2  5  2  3  3  2  i s made.  As may be seen from the examples quoted above a d i f f e r e n t i a t i o n between monodentate and bidentate bridging S0 X groups i s possible 3  even through the symmetry of both i s C_.  In the SO- s t r e t c h i n g  region 0 0 there i s a d e f i n i t e d i f f e r e n c e . In the monodentate case, i . e . S * X 0 where 0 i s the bonding oxygen, there are three s t r e t c h i n g modes. s  S0 - as (A")  S0 sym(A') and  2  S0*(A').  2  J  The p o s i t i o n of the l a s t  mentioned band i s dependent on the nature of the group "E" to which O 0- E the 0* i s bonded. On the other hand i n the bidentate c a s e , S * X *0-E where again 0 i n d i c a t e s the bonding oxygens there are 3 d i f f e r e n t S-0 s t r e t c h i n g bands.  These are v S 0 ( A ' ) , VSO* as (A") and ^S0*sym (A ) 1  Here the p o s i t i o n of VSO i s independent of the moiety to which the S0 X i s bonded and the p o s i t i o n of the other two modes i s  dependent  3  on the nature of E.  By comparing s p e c t r a , the s h i f f c l of one SO  s t r e t c h i n g mode o n l y , i n d i c a t e s a monodentate S0 X group while the 3  s h i f t i n g of two modes i s a good i n d i c a t i o n of a bidentate S0 X group. 3  The p a r t i c u l a r case of the S 0 C F 3  the assignment of C F S 0 C F 3  3  3  group w i l l be considered l a t e r i n  3>  In summary, these are the ways i n which the v i b r a t i o n a l spectra of S 0 C F - I compounds w i l l be s t u d i e d . 3  3  Assignments of the  spectra w i l l be made with reference to the study of the anion by 21 Burger et a l .  and the published spectra of covalent S0 CF 3  3  groups.  The d e c i s i o n of whether or not the compound contains i o n i c S 0 C F 3  3  groups w i l l be made on the basis of the number of SO., modes present.  58.  TABLE 5 A comparison of SO^X i n f r a r e d v i b r a t i o n a l frequencies in (C H ) 2  5  2  Sn(S0 F) 3  5  and C C H ) 2  (C H )  (C H ) Sn(S0 F) 2  2  2  3  *  5  2  5  2  Sn(S0 CF ) 3  Sn(S0 CF ) 3  3  3  2  2 3  Assignment  2  -1 cm  intensity  1360  vs, b  1340  vs, b  S0  3  s t r e t c h (A")  1170  vs, b  1138  s, b  S0  3  stretch  (A )  1070  s  1036  vs  S0  3  stretch  (A')  612  m, sh  632  s  S0  3  bend (A")  585  s , sh  581  m  S0  3  bend (A )  575  s  512  s  S0 X; bend (A )  416  ms  356  m  S0 X  355  m  320  ms  S0 S t o r s i o n  -1 cm  intensity  Term meanings: vs - very strong  s - strong  m -•medium  vw - very weak  b - broad  sh -  shoulder  w - weak  1  1  1  3  3  3  rock  59.  Whether a compound contains monodentate, b i d e n t a t e , or both monoand bidentate SO^CF^ groups w i l l be decided by comparing the spectra with spectra of compounds known to contain mono- or bidentate SO^CF^ groups.  These and other features of the spectra w i l l be discussed  i n conjunction with the analogous f l u o r o s u l f a t e compounds.  Finally,  because of the complex symmetry of the SO^CF^ group i t should be noted, from a purely p r a c t i c a l point of view that a l l v i b r a t i o n a l modes should be both Raman and Infrared a c t i v e . 2 M[I(S0 CF ) ] 3  3  4  The v i b r a t i o n a l frequencies observed f o r Rb[I(SG* CF ) ] are 3  3  4  l i s t e d , along with estimated i n t e n s i t i e s i n t a b l e 6 as w e l l as 56 the S 0 C F v i b r a t i o n s found f o r (CH ) GeS0 CF 3  3  3  3  3  that because of the unreactiveness of the S0 CF 3  .  3  3  It i s i n t e r e s t i n g  compound the i n f r a r e d  spectrum was obtained below the s i l v e r h a l i d e region in contrast to the s i t u a t i o n f o r I-SO^F compounds.  The assignment of the spectra 21  i s based mainly on the assignment by Burger et a l .  . The small  s p l i t t i n g of the absorption bands f o r the [ I ( S 0 C F ) ] ~ ion which 3  3  4  are p a r t i c u l a r l y obvious i n the Raman spectrum in the S-0 and C-F s t r e t c h i n g range ^ { i r a t t r i b u t e d to s o l i d s t a t e s p l i t t i n g caused probably by weak coupling of the i n d i v i d u a l S 0 C F 3  3  groups.  Precedent f o r such s p l i t t i n g s are found i n a number of f l u o r o s u l f a t e - 59 anions, i . e .  [I(SO^F)^]  .  Many features observed in the spectrum  of R b [ I ( S 0 C F ) ] , such as the very broad i n f r a r e d absorption bands 3  3  4  and the discrepancies i n p o s i t i o n between the i n f r a r e d and Raman  Table 6  GO.  V i b r a t i o n a l Frequencies f o r Rb [KOSC^CF.^] and  Rb[I(OS0 CF ) 2  Raman fern ^"1  3  (CH ) 3  3  Ge OS0 CF 2  3  (CH ) GeOS0 CF 3  4'  Infrared  \cm ^]  3  Infrared  2  [cm  3  Approximate d e s c r i p t i o n  1376 mw 1368 w  1365 vs,b  1365 s  v  1251 m 1234 mw  1242 s sh  1241  v  1214 w  1210 vs.b  1205 vb  v  1170 ms  1150 s,b  1164 s  v  1074 vw  ~1080 vwjsh  as  S0 2  as  CF_ 3  o  sym as  S0„ 2  CF. 3  impurity of I(0S0 CF > 2  974 vw 854  865 s.sh 830 v s , b  984 vs,b  vS-OX  777 vs  770 s  768 m  vCS  632 s,b  634 s  6S0  620 ms  615 m,sh  620 m,sh  S0  598 vs  590 m  590 s  6  576  578 w  572 ms  6S0 X  536 s  528 s  515  6 CF. as 3  515 sh  510  652 ms  2  642 w  435 ms  rocking  2  sym  CF„ 3  2  v  as  *  10  408 w 394 s  vIO sym i n phase  383 ms  vIO sym out of phase  346 ras  352 vs  pso  322 s  315 ms  | 6CS  2  264 ms 253 w  PCF  3  3  61. bands are a l s o present f o r FXeSO^CF^, i n d i c a t i n g a strong s t r u c t u r a l similarity.  There a r e , nevertheless, some differences in the proposed  assignments. The three sulfur-oxygen v i b r a t i o n s expected f o r a monodentate SO^CFg group are found at  1365, 1210 and 850 cnf^.  This i s in  r e l a t i v e l y good agreement with corresponding bands f o r except f o r the 850 cnf^ band which i s assigned to  (CH^GeSOgCFg  S-OX and i s  d e f i n i t e l y a f f e c t e d by the e l e c t r o n e g a t i v i t y of the group X. comparable bands f o r FXeS0 CF are at 3  3  1390,  1200, and  The  840 c m  -1  55 respectively  .  The C-F s t r e t c h i n g modes are found at 1251, 1234, and 1 1 7 0 . c m , -1  a region s i m i l a r to that f o r the SO^CF^ i o n .  This i n d i c a t e s that the  CFg group i s l i t t l e a f f e c t e d by the bonding through oxygen. l o c a l symmetry f o r the CF  3  moiety remains C  3 v  The  and i s not reduced.  The number and p o s i t i o n of the s t r e t c h i n g modes i s i n every way cons i s t e n t with a monodentate SO^CF^ group. In the region of the bending modes good agreement between the f i n d i n g s f o r R b [ I ( S 0 C F ) ] and both (CH ) GeS0 CF 3  found.  3  4  3  3  3  3  and FXeS0 CF 3  3  is  The i n f r a r e d and Raman spectra are well resolved and c o n s i s t e n t _i  in this region.  The only exception occurs around 400 cm  .  Bands  of f a i r l y high i n t e n s i t y which occur at 394 and 383 cm"^ i n the Raman spectrum are absent in the i n f r a r e d spectrum while a band at 435 cm"^ only appears i n the i n f r a r e d spectrum.  The two Raman bands are  assigned as the symmetric in phase and out of phase 1-0 s t r e t c h i n g modes.  The 435 cnf^ band i s assigned as the asymmetric 1-0 s t r e t c h i n g  62. mode.  This mutual exclusion i s what i s expected f o r a square planar 60  c o n f i g u r a t i o n around i o d i n e .  Several precedents have been reported  where the asymmetric s t r e t c h i n g band occurs at a higher wave number than the two symmetric bands.  However, t h i s i s not found f o r  ICl^  The p o s i t i o n s observed f o r the [ I ( S 0 C F ) ] ~ ion are s l i g h t l y lower 3  3  4  than those observed f o r the [ I ( S 0 F ) ] " i o n . The extremely low 1-0 - 39 s t r e t c h i n g modes found f o r [ I ( C 1 0 ) ] are unusual but may perhaps be due to a very weak 1-0 bond. This i s i n d i c a t e d by the low thermal 39 s t a b i l i t y (up to room temperature) of C s [ I ( C 1 0 ) ] compared with 3  4  4  4  4  4  the thermal s t a b i l i t y of the [ I ( S 0 F ) ] " and [ I ( S 0 C F ) ] ~ ions which 3  4  3  3  4  39 can be as high as 200°C.  This trend i s also found f o r I ( C 1 0 ) 4  s t a b l e up to -45°C and I ( S 0 C F ) 3  above 170°C.  3  3  1  which begins to decompose only  The spectra of K [ I ( S 0 C F ^ ) ] and 3  C s [ I ( S 0 C F ) ] presented an almost i d e n t i c a l p i c t u r e . 3  ,  The iodine oxygen deformation modes which should occur  below 200 cm" were not observed. 3  3  4  4  Only very minor  discrepancies were observed. 3.  I(S0 CF ) 3  3  3  The assignment of the spectrum of I ( S 0 C F ) 3  3  presents a more  3  complex problem than was encountered f o r I(SO^CF^)^ . -  This i s seen  by the increased number of bands observed i n the S-0 and C-F s t r e t c h ing region from 1450-700 c m . - 1  There are ten bands assignable as  fundamentals i n the spectrum of I ( S 0 C F ) ~ while there are 14 3  bands f o r I ( S 0 C F ) . 3  3  3  3  4  The d i f f i c u l t y in assigning these bands i s  increased by the f a c t that many of them are extremely broad in the i n f r a r e d spectrum.  In a d d i t i o n , accidental coincidence of bands,  sensitivity 1 x 5 0 0  64.  p a r t i c u l a r l y in the 1280-1150 c m complications.  -1  region may present a d d i t i o n a l  Because of t h i s complexity only approximate a s s i g n -  ments of the S-0 and C-F s t r e t c h i n g modes dinz possible and some ambiguity i s unavoidable.  The complexities observed are most l i k e l y  due to SO^CFg groups of d i f f e r e n t f u n c t i o n a l i t y .  The i n f r a r e d and  Raman spectra are l i s t e d i n table 7. Bands occuring at  1420,  1210 and  830 cm  are assigned  as S-0 s t r e t c h i n g modes f o r a monodentate SO^CF^ group.  This a s s i g n -  ment i s based mainly on the s i m i l a r i t y of these bands to the c o r r e s ponding bands f o r U S O ^ C F ^ ) ^ . numbers f o r v S 0  2  The s h i f t to s l i g h t l y higher wave-  i s a l s o observed i n the corresponding  fluorosulfate  compounds and may r e f l e c t the e l e c t r o n i c d i f f e r e n c e s between a neutral species and an anion.  The bands at -1320, 1120, and 980 cm"  on the other hand are remarkably s i m i l a r to sulfur-oxygen  stretching  bands f o r a bidentate b r i d g i n g SO^CF^ group as found i n both ( C H ) 3  Sn S 0 C F 3  3  5 4  and ( C H ) 3  2  Sn(S0 CF ) 3  t h i s region a t 1240, modes.  3  2  1 8  .  and^f^-cm"  3  reasonable to assume that the CF  3  the environment of the S 0 moiety. 3  1  are assigned to CF s t r e t c h i n g  3  groups.  However, i t seems  groups are not a f f e c t e d much by A l l of these bands occur as  shoulders i n the i n f r a r e d spectrum (see table 7) and any s p l i t t i n g may be e i t h e r too small to be observed or obscured by the adjacent broad S 0 bands. 3  3  The remaining three bands i n  It might be expected that these bands should occur at d i f -  ferent wavenumbers f o r d i f f e r e n t S0 CF  1  Table 7  65.  V i b r a t i o n a l Spectrum of I ( 0 S 0 C F ) 2  Raman -1,  r  IR I n t  '  Approximate  -1  I n t  *  f 1 1420 s,b  1321 m  1324 ms  vSO(br)  1240 ms  1235 m,sh  vCF  1208 mw  1210 vs, b  '1160 w.sh  1165 w,sh  v S0 (t) sym 2 vCF  1120 s  1130 s,b  vSO(br)  1084 s  1090 s,sh  vCF  m  c  Raman 1  l J 1435 m,sh 1427 ms c  description v S0„(t)  m  a  s  3  3  IR I n t  -  Approximate  i  Int.  [cm ] 619 vs  [cm ] 625 s,b  568 vw  580 ms.sh  549 s  542 w,sh  513 w  515 s  description  X  2  3  o  452  w  3  3  993 mw  980 ms  vSO(br)  818 vs  830 vs,b  vSO  414 w  415 w  393 s 361 361 358 s  390 s 362 s  327 s  318 s  275 s 269 s  793 w 780 vs 768 w  780 s,b  729 vw  730 s,b  vSC  "  640 w  \  66.  As was explained f o r R b [ I ( S 0 C F ) ] a square planar c o n f i g u r a 3  3  4  t i o n of oxygen around iodine i s to be expected. of I ( S 0 C F ) 3  3  3  However, in the case  i t i s not p o s s i b l e to make a d e f i n i t e assignment of the  1-0 s t r e t c h i n g bands based on a square planar arrangement. the bands observed in the region from 430-380 c m Raman a c t i v e .  -1  Almost a l l  are i n f r a r e d and  This may be due to a d i s t o r t i o n of the square planar  arrangement of oxygen caused by the presence of two non-equivalent S0 CF 3  groups.  3  4.  IS0 CF 3  3  For t h i s very dark red brown compound no Raman spectrum was obtained, despite repeated attempts on several d i f f e r e n t samples. i n f r a r e d spectrum i s very complex.  The spectrum i s l i s t e d i n t a b l e 8.  Although the spectrum i s very complex and d i f f i c u l t to assign i t different IS0 CF 3  of -I  3  fo^the  is  spectra f o r I ( S 0 C F ) , ( I ( S 0 C F ) ] " or S 0 C F " . 3  3  3  3  3  4  3  3  i s , t h e r e f o r e , a unique compound rather than merely a mixture  and I ( S 0 C F ) . 3  or I ( S 0 C F ) +  The  3  3  3  3  Unusual i o n i c formulations such as I [ I ( S 0 C F ) ] ~ 3  are a l s o h i g h l y u n l i k e l y .  a polymer with polydentate S 0 C F groups. 3  3  +  3  The m o s t l i k e l y s t r u c t u r e i s Any assignment of the  i n f r a r e d spectrum i s d i f f i c u l t and a more d e t a i l e d d e s c r i p t i o n of the structure would only guesswork.  The I in ISO^CF should be p o s i t i v e l y  p o l a r i z e d and extensive a n i o n - c a t i o n i n t e r a c t i o n could r e s u l t . x - r a y d i f f r a c t i o n study on the two m o d i f i c a t i o n s of IC1  The  may serve  as an i l l u s t r a t i o n f o r complications which may be expected in such a case.  3  4  TABLE 8 V i b r a t i o n a l Spectrum of ISO^CF  infrared ,  cm  1340  w, sh  1210  vs  1135  j. b m  1025  *  930  m  770  ms  684  m, sh  624  ms , b  585  m, sh  555  sh  518  ms  455  vw  371  m, sh  358  vs  338  m, sh  312  ms  * For explanation of terms see Table 5  68. 5.  IBr.,SO,CF The spectra of IBr^SO^CF^, l i s t e d i n table  9  w i l l be considered  + as derived from I B r interaction.  and SO^CF^  2  with allowance f o r some c a t i o n - a n i o n  This treatment i s based on studies of analogous f l u o r o -  6 s u l f a t e compounds .  — In considering the SO^CFg" anion spectra the  assignments of Burger et al  21  w i l l be used, while the I B r  + 2  cation  spectrum w i l l be compared with the spectra of other compounds c o n t a i n ing the I B r  2  +  cation.  In contrast to the interhalogen  which were found to react with most conventional  fluorosulfates^  l . R . window materials  gave well resolved i n f r a r e d spectra with both AgBr and KRS-5  IB^SO-JCF-J  windows and spectra were recorded down to 200 c m " . 1  More anion bands were observed f o r IB^SO-jCF^ than were observed by Burger f o r AgSO^CFg.  This most l i k e l y i s due to the removal of  the degeneracies of the E modes of the S 0 and CF 3  3  vibrations.  In  p a r t i c u l a r a n i o n - c a t i o n i n t e r a c t i o n would r e s u l t in the s p l i t t i n g of the S 0 modes, and t h i s i s the most l i k e l y source of a d d i t i o n a l bands. 3  The I B r  2  +  c a t i o n , u n l i k e the A g  +  c a t i o n , i s not s p h e r i c a l and some  symmetry lowering due to t h i s asymmetry may s p l i t the CF  3  modes as  well. The only major changes f r o m t h e assignment made by Burger i s f o r the CF  3  s t r e t c h i n g frequencies.  Burger assigns the band at 1237 cm~^  as ano- A mode and the band at 1167 as an E mode.  Spectra f o r  IBr S0 CF 2  i n d i c a t e that the band at 1237 i s s p l i t and thus the A and E modes should be interchanged. made with other CF  3  Burger bases his assignments on comparisons  containing compounds.  In every other case the A  3  3  69.  TABLE 9 Infrared Spectra of I B r S 0 C F 2  IBr S0 CF 2  3  S 0  3  3 3~ C F  i n  3  A  g  s 0  and AgS0 CF  3  3  3  C f :  21 3  Approximate description  *a 1400, vw, sh  comb, band  1280 v s , b  1270 v s , b  S-0 s t r e t c h  1220 s , sh  1237 s  CF s t r e t c h  1205 vs  CF s t r e t c h  1165 s , sh 1025 s (1026m) ) b  1167 s  CF s t r e t c h  1043 vs  S-0 s t r e t c h  935 vw  comb.  770 ms (770w) ) b  760 m  650 m, sh  C-F s t r e t c h 0-SO bend  625 vs  647 s  C SO bend  580 ms  582 m  FCF bend  565 W, sh  579 sh  Comb, band  525 s  525  0S0 bend  515 s  515.  0S0 bend  360 vw, sh  Comb, band  345 s (354) )  351 m  C - S - 0 bend  315 ms 258 s (260s) ) ' \ 248 s ( 2 5 3 v s )  320 m  F-C-F bend S . . . IBr stretch  215 m  217 s  b  b  v  D  h  0  D;  d  a.  For explanation of terms see t a b l e 5,  b.  Raman Spectrum  F-C-S bend  70. mode occurs at a lower wavenumber than the E mode. case where the E mode i s lower.  SO^CF^" i s the only  It would seem reasonable, t h e r e f o r e ,  i n view of the s p l i t t i n g observed f o r IB^SOgCF^ to interchange the two assignments. The CFg s t r e t c h i n g bands occur at 1220, 1205 and 1165.  The SO^  s t r e t c h i n g modes which are expected to be s p l i t more than the CF^ bands occur at 1280 and 1025.  The band at 1280 which i s assigned to  the E mode f o r SO^ i s very broad and some s p l i t t i n g is' i n d i c a t e d . That the SO^ bands are broader than the CF^ bands has been observed 22 f o r other SOgCF^ compounds  .  The bending modes occur much as would be expected f o r an SO^CF^" ion.  The only d i f f e r e n c e i s that the SO^ E mode i s s p l i t .  bending v i b r a t i o n s occur at  650,  bending v i b r a t i o n s occur at between 1400 and 300 c m  -1  525 and  580 and  515 c m " , while the CF 1  315 c m " . 1  1  -1  except  These bands are very weak  and are assigned as combination bands of the SO^CF^" i o n . two bands at 258 and 246 c m  3  A l l the other bands  can be assigned to SO^CF^" v i b r a t i o n s  f o r three bands at 1400, 935 and 565 c m " .  tions.  The SO^  The remaining  are assigned as IBr^ s t r e t c h i n g v i b r a -  As can be seen from table 10 bands in t h i s region agree quite  well with the bands assigned f o r IB^SO^F.  Unlike the case f o r  IB^SOgF, however, the I B ^ s t r e t c h i n g modes appear to be s p l i t into a symmetrical and an asymmetrical band. would be expected f o r a bent IBr^  group.  Both are Raman a c t i v e , as When discussing t h e i r  f i n d i n g f o r IB^SO^F, where only one IBr s t r e t c h was observed i n the Raman spectrum, Wilson et a l . invoked accidental degeneracy f o r the  71  TABLE 10 V i b r a t i o n a l frequencies f o r I B r  Compound  IBr S0 CR 2  3  IBr S0 F 2  3  v lBr asym. 2  3  2  +  in IB^SO^CF^ and IBr^SO^F^  v iBr  2  sym  <5IBr  2  258 cm"  1  248 c m  256 cm"  1  256 cm" '  -1  1  127 cm"  1  72. two s t r e t c h i n g modes (a s i t u a t i o n which had been previously found f o r + 63 Br^  ) rather than a l i n e a r cation where only one band would be  Raman a c t i v e .  The r e s u l t s f o r IBr^SO^CF^ c l e a r l y point to a bent  t r i atomic cation as would be expected using a simple valence e l e c t r o n p a i r repulsion treatment.  The only remaining band at 215 cm  is  assigned to an S - C - F bending mode. 6.  I0 S0 CF 2  3  3  Iodyl trifluoromethanesulfonate i s a very good Raman s c a t t e r e r and a well resolved Raman spectrum was obtained.  The i n f r a r e d spec-  trum obtained on a f i n e l y powdered sample held between two s i l v e r bromide plates was a l s o w e l l r e s o l v e d . two main features were considered.  In assigning the spectra  For the S0 CF 3  3  group,  attention  was focussed on the S-0 and C-F s t r e t c h i n g region while for the I 0 moiety a comparison with other iodyl s a l t s was made. frequencies of I0 SG" CF 2  3  3  2  The band  and the assignments are l i s t e d in table 11-  For the SO^CF^ group, the presence of three S - 0 s t r e t c h i n g modes at  1326, 1221 and 941 i n d i c a t e that the S 0 C F 3  i n t e r a c t i n g with the I 0  2  3  group i s  and i s not j u s t a simple S0 CF ~ i o n . 3  The  3  p o s i t i o n of the bands i s compatible with e i t h e r a monodentate or b i dentate bridging group, but the f a c t that only 3 bands occur would suggest that only one type of S 0 C F 3  3  group i s i n v o l v e d .  s t r e t c h i n g frequencies are at 1225 and 1125 c m " . 1  The CF  3  The lack of  s p l i t t i n g of the E mode suggests that they r e t a i n a l o c a l C V 3  symmetry.  Again the other bands have been assigned by comparison  73. TABLE 11 V i b r a t i o n a l frequencies f o r I 0 S 0 C F 2  I0 S0 F 2  3  -1 Raman Cm  I0 S0 CF 2  3  3  3  and I 0 S 0 F 2  3  Approximate Description  3  -1 Raman Cm  -1 IR Cm  Int.  1424 vw 1335 1195  1326 ms "  1332 s  S0  1233 m  1225 s , sh  CF  1221 mw  1210 s  S0  3  1125 s  1125 s  CF  3  S0  3  a  3  3  str sym s t r . str.  1170 1070  as. s t r .  1055 w, sh str,  1030  975 w  965 m, sh  1010  941 s  938 s  878  849 ms  860 vs  I0  2  as.  865  823 vs  830 vs  I0  2  sym. s t r .  900  843  S-F s t r . 774 ms  780 m  678 s  680 w, sh  660  645 m  642 s  615  628 w  630 s , sh  589 ms  600 s , sh  578 m  585 s , sh  542 s  540 s  522 ms  520 m, sh  S-C s t r .  459 ;428 415  310  395 s 367 w, sh  360 ms ,  345 s  340 m, sh  328 ms  320 w, sh  311m continued.  str.  TABLE 11, continued  I0 S0 F 2  3  I0 S0 CF 2  3  3  290 m 258 ms 235 vs 217 mw 190 vs 163 m 115 w, sh  a.  For explanation of terms see table  74.  to the assignment of Burger et a l . 780 cm  1  21  on the SO^CF^  ion.  The band at  which i s c h a r a c t e r i s t i c of the SO^CF^ group i s present and  i s not s p l i t .  This i s f u r t h e r evidence f o r only one type of S 0 C F 3  3  group. The iodine oxygen s t r e t c h i n g v i b r a t i o n s occur i n ^ S O - ^ F at 878 and 865 cm" in the Raman Spectrum.  In the corresponding IOgSO-^CF-j  1  these same bands are at 823 and 849 c m " .  A l l i n d i c a t i o n s are that  1  the 10^ group in the S0 F compound i s s i m i l a r to the same group i n 3  the S 0 C F compound. 3  S t r u c t u r a l proposals f o r ^ S O - ^ F and several  3  fid  other I0£ compound are given by Carter and Aubke  .  Based on v i b r a -  t i o n a l spectra and s o l u t i o n studies they suggest that d i s c r e e t groups are associated by bridging anions. which occur between 800 and 950 c m  -1  10 f o r I0F  5  2  +  The s t r e t c h i n g frequencies  are i n d i c a t i v e of an iodine oxygen  -l m u l t i p l e bond e . g .  I0  fi5  i s 927 cm  .  The r e s u l t s  for  IOgSO^Fg agree with these s t r u c t u r a l proposals.  In c o n c l u s i o n , a s s o c i a t i o n over 1 - 0 — I very s l i g h t judging from the p o s i t i o n of  bridges i s probably -  The obvious polymeric  nature of the material must, t h e r e f o r e , be due to anion bridging between d i s c r e e t 10^ groups.  The p o s i t i o n of the t h i r d S-0  s t r e t c h i n g mode at 940 cm" i s somewhat lower than f o r the same 1  band i n (CH ) SnS0 CF where 3  3  3  3  a bidentate bridging group i s present.  The r e l a t i v e l y low p o s i t i o n of t h i s band i n IO^SO^CF^ seems to i n d i c a t e p r e f e r e n t i a l bonding to one 10^ group (a) rather than i d e a l  Figure 9  75.  Infrared Spectra of (10) S0 CF and 3  (I0 ) 2  (I0 )S0 CF 2  3  3  S O 3 C F 3  3  from 1 5 0 0 - 2 5 0 cm"  1  76.  bridging (a)  (b),  ,10  0 I 2  (b)  2  2  0 ^ . — 0  o—s—o'  /\  0  CF  10,  0 I,  0  3  A  CF  3  The large number of bands i n the spectra are presumably due to extensive coupling of v i b r a t i o n a l modes and a more d e t a i l e d assignment of the spectra i s not p o s s i b l e . 7.  I0S0 CF 3  3  We'll resolved i n f r a r e d and Raman spectra were obtained f o r 1  I0S0 CF . 3  The v i b r a t i o n a l frequencies and the proposed assignments  3  are given i n table 12. center on the S0 CF 3  The S0 CF 3  3  3  The discussion of the assignments w i l l again  group and the 10 s t r e t c h i n g frequencies.  group i s not merely an anion with C V symmetry. 3  The s p l i t t i n g of the E mode S-0 s t r e t c h i n g frequency i n d i c a t e s a lowering of symmetry by a s s o c i a t i o n through the oxygen. s t r e t c h i n g bands at  1390,  1210 and  970 c m  unsymmetrical bidentate b r i d g i n g S 0 C F 3  f o r IOgSOgCF^)  The CF  3  3  -1  group.  are assigned to an (See the d i s c u s s i o n  s t r e t c h i n g f r e q u e n c i e s , found at  1133 c m , i n d i c a t e the l o c a l symmetry of the GF - 1  The S-0  3  1242 and  group remains C v . 3  The lower frequency bending and deformation region below 1000 cm  1  has a large number of bands i n d i c a t i n g an extensive degree of v i brational coupling between d i f f e r e n t v i b r a t i o n a l modes. only an approximate d e s c r i p t i o n of the bands.  This allows  The attempted a s s i g n -  77. TABLE 12 V i b r a t i o n a l Frequencies f o r IOSO^CF^  Raman cm  1  Approximate Description  Infared  intensity  cm  -1  intensity  1420  vw  1390  ms  1395  w  1284  ms  1280  ms  1242  m, sh  1240  ms  1214  ms  1210  s  1133  s  1140  vs  1018  s,b  1040 1025  a  s ms  970  m  883  vs  885  s  vw  860  s  s  777  ms  670  m, sh  s  655  m, sh  s  640  s  ms  625  m, sh  s  585  m, sh  w  550  s  s  528  s  vs  455  w,b  662 624 587 560 535 529 453 380 360 355  w, sh  418  mw  ms  375  m, sh  m  > 350  m, sh  320  w, sh  329  m  316  m  290  m  248  ms  155  vw  a.  3  S0 as.CF  stretching stretching  3  stretching  3  stretching  S0  3  stretching  10 s t r e t c h  865  634  sym.CF  3  w, sh  969  779  S0  For explanation of terms see table 5  S-C s t r e t c h  78.  ment i s given i n t a b l e 12.  Notice that once again the c h a r a c t e r i s t i c  band at 777 cm" i s present as a s i n g l e band i n d i c a t i n g the presence 1  of only one type of SO^CF^ group. S t r u c t u r a l proposals f o r iodosyl compounds have been based mainly on a polymer of ( I 0 ) "  u n i t s surrounded by anions.  +  The main  t h r u s t of t h i s proposal comes from the rather low 1-0 s t r e t c h i n g frequencies found f o r most iodosyl s a l t s .  As mentioned before in the  case of IG^SOgCFg an iodine oxygen double bond would r e s u l t i n a s t r e t c h i n g frequency between 800 and 900 c m  -1  while as has been shown  f o r several iodosyl compounds the 1-0 s t r e t c h i n g frequencies occur somewhat lower, around 600 cnf . the chain polymer f o r ( I 0 ) S 0 2  as f o r I 0 2  4  4  Dasent and Waddington  and ( I 0 ) S e 0 2  4  proposed  on t h i s bas?s as well  Subsequent to the preparation of IOSO^C^ the iodosyl CO  f l u o r o s u l f a t e I0S0 F was a l s o prepared  .  3  to t h i s general d e s c r i p t i o n . were much lower than 800 c m  It was found to conform  That i s , the s t r e t c h i n g frequencies -1  and a chain polymer of I 0  +  units i s  proposed. For IOSO^CFg, however, there are no s u i t a b l e v i b r a t i o n s i n the region from 550-600 cm" which could be assigned as 1-0 s t r e t c h i n g 1  bands.  Two bands at  860 and 885 cm" are assigned as vIO. 1  s p l i t t i n g i n t o two bands i s due to s o l i d s t a t e e f f e c t s . I0F  3  which has been shown by an x - r a y d i f f r a c t i o n s t u d y  a short 10 bond has  1-0 at 883 cm"  ing frequency i s found at 927 c m " . 1  1  6 4  .  In I0F  c  6 5  The  The compound 67  to contain  the 1-0 s t r e t c h -  Several d i f f e r e n t 1-0 s t r e t c h i n g  frequencies which have been found are shown in t a b l e 13.  The  79.  Table 13 1-0 s t r e t c h i n g frequencies in several compounds Compound (I0) S0 2  4  V  6 6  (I0) Se0 2  IOSOgF  53  I0S0 CF 3  3  4  I 0 cm" j^ , 2  proposed s t r u c t u r e chain polymer chain polymer  6 6  650  chain polymer  °°Q  d i s c r e t e 10 groups  907  d i s c r e t e 10 groups  927  d i s c r e t e 10 groups  64 I0F  3  64 I OF,-  80. s i n g u l a r l y high VIO f o r IOSO^CF^ would seem to i n d i c a t e the presence of d i s c r e e t 10 units in IOSO^CF^ as opposed to polymeric 10 s t r u c t u r e s f o r other iodosyl compounds. In comparing t h i s f i n d i n g to the s i t u a t i o n f o r IOSO^F i t must be concluded that any extensive 1 - 0 — I f o r the IOSOgCF^.  It should be kept i n mind that a l l previous 10  s a l t s ; (I0) S0 , (I0) Se0 2  a s s o c i a t i o n i s absent  4  2  4  and (I0)S0 F- have r e l a t i v e l y small anions. 3  The l a r g e r anion i n IOSO^CF^ may prevent the formation of bridges in the compound. IOSO^CHg or IOCO^jCFg.  1-0—I  A s i m i l a r s i t u a t i o n would be expected f o r  However, as mentioned previously a l l attempts  to obtain these compounds have been unsuccessful to t h i s p o i n t . In conclusion f o r the v i b r a t i o n a l spectra of a l l the I-SO^CF^ compounds studied im t h i s work there i s a complete analogy to the spectra of the corresponding f l u o r o s u l f a t e s except f o r the rather unique case of the iodosyl compounds. CF^SOgCF^ jrif1uoromethy1  8.  trifluoromethanesulfonate 25  This compound had already been reported by N o f t l e and Cady who also l i s t i n f r a r e d frequencies in the NaCl r e g i o n .  In t h i s work  the thermal decomposition of I(S0gCF )g was found to y i e l d CF^SOgCFg 3  as a v o l a t i l e product.  The v i b r a t i o n a l spectrum of C F S 0 C F 3  3  3  is  i n t e r e s t i n g i n that i t may be expected to provide an example of a monodentate covalent trifluoromethanesulfonate group.  Only l i m i t e d  information on v i b r a t i o n a l spectra of t h i s monodentate group are 25 available  .  The spectrum should i l l u s t r a t e several arguments which  have been invoked p r e v i o u s l y regarding the d i f f e r e n c e s in f u n c t i o n a l i t y  81.  Table 14 V i b r a t i o n a l Spectra of CF^SO^CF^  This work Raman cm 1470  1  infrared cm  Reference no. 25 -1  infrared cm  *  w 1460 w  Assignment  -1  not assigned 1462 s  1461 s  S0  2  asym. s t r e t c h  1370 w  not assigned  1350 w  not assigned  1272 s  1270 s ,sh  502 sym. s t r e t c h  1253 w,sh  1262 vs  1258 s  CF3-O asym. s t r e t c h  1228 vw  1232 vs  1230 s  CF3-S asym. s t r e t c h  1154 s  1150 w,sh  1130 m,sh  1135 vs  CF3-O sym. s t r e t c h 1134 s  503 impurity  1074 954 w  950 s  954 s '868 vw  S-0* s t r e t c h not assigned S-C s t r e t c h  805 m 770 vs  CF3-S sym. s t r e t c h  785 m  786 m  CF3-S bend  760 w  766 m  not assigned  745 w  not assigned  715 w  not assigned  610 vw  620 m,sh  SO3 asym. bend  585 m  595 m  CF3 deformation  580 m,sh  CF3 deformation SO3 deformation  547 m 528 w 490 w,sh 397 w 349 ms 325 m 305 m 281 s  -  82.  of the SO-jCFg group.  The i n f r a r e d and raman spectra of CF^SO^CF^  obtained by thermally decomposing I ( S O ^ C F . ^ (irJ-reported  i n t a b l e 14.  along w i t h the i n f r a r e d bands reported by N o f t l e and Cady. The main i n t e r e s t in the v i b r a t i o n a l assignment of SO^CF^ groups of d i f f e r e n t f u n c t i o n a l i t i e s i s i n the unambiguous i d e n t i f i c a t i o n of the S-0 s t r e t c h i n g frequencies.  The observed p o s i t i o n s should  be comparable to those f o r the f l u o r o s u l f a t e group.  The CF^ p o s i t i o n s  are only of secondary i n t e r e s t as the group may be expected to r e t a i n l o c a l C^V symmetry regardless of the symmetry of the f u n c t i o n a l i t y with only small s p l i t t i n g s of the degenerate E modes. In summarizing the monodentate, b i d e n t a t e , and and SO^F cases the ranges expected f o r  ionic  SO^CF^  S-0 are shown i n table'"15.  along with the assignment f o r CF^SO^CF^.  The presence of two d i f f e r e n t  CF^ groups i n one molecule i s detectable in the s t r e t c h i n g region o n l y . Overlap and superposition of bands obscure the deformation r e g i o n . The SOg s t r e t c h i n g frequencies are c l e a r and the assignment i s c l e a r i n the region from 830-1500 c m . - 1  For the i o n i c SOgX group (X being C F o f F ) , the symmetry of 3  the S 0 moiety i s C v and there are only two S 0 s t r e t c h i n g modes, 3  3  3  a degenerate E mode and an A respectively.  1  mode.  These occur at  1260 and  1050 cm"  1  For a monodentate SO^CFg group the symmetry i s lowered  to C,- and the E mode i s no longer degenerate.  The two bands obtained  from the s p l i t t i n g of the E mode can be considered as an S 0 asymmetric 2  s t r e t c h between 1470  and  1370 c m  between 1180 and 1270 c m . - 1  SO  s t r e t c h where the 0  -1  and an S0^ symmetric s t r e t c h  The A' mode can now be thought of as an  i n d i c a t e s the oxygen through which bonding  1  83. Table 15 S-0 s t r e t c h i n g frequencies in i o n i c , monodentate, and bidentate S0 F and S0 CF 3  3  GROUP  Ranges f o r vS-0 cm  ionic  E mode  S0 F 3  S0 CF 3  3  S0 F 3  S0 CF 3  3  A-j mode 1080  1260  1050  VSO2 symmetric 1200-1250  980-850  1370-1470  1180-1270  950-830  >*S0 symmetric 2  S0 F 3  VSO  1400-1500  *  bidentate  -1  1280  VSO2 asymmetric  monodentate  groups.  3  V SO  V S 0 asymmetric 2  S0 CF 3  3  CF S0 CF 3  3  3  1300-1380 1461  1145-1220  1000-1060  1270  950  84. occurs.  This band i s considerably lowered and occurs between 830 cm  and 950 c m . - 1  1  F i n a l l y , for the bidentate S0 CF group the symmetry i s 3  3  also C and the E mode i s s p l i t . The two bands derived from the E s * * mode can be considered as SO ^ s t r e t c h e s , here 0 referes to the two r  oxygens through which bonding occurs.  The bands are considerably  lowered compared to the u n s p l i t E mode of the i o n .  The asymmetric band  occurs between 1300 and 1380 cm" and the symmetric between 1145 and 1  1220 c m . - 1  The A  mode, an S-0 stretch^occurs between 1000 and 1060 cm a-J'f -1  1  not changed too much from the i o n i c p o s i t i o n . S0 CF 3  3  modes.  Note that a t r i d e n t a t e  group would again have C*v symmetry and have two S-0 s t r e t c h i n g 3  These modes should occur considerably lower than they would  f o r an i o n i c S 0 C F 3  3  group.  Comparing the SO v i b r a t i o n a l band assignments f o r C F S 0 C F 3  3  3  with  the scheme o u t l i n e d above and summarized i n t a b l e if we can see that i t f a l l s neatly w i t h i n the monodentate group with a l l bands at the upper l i m i t s .  This treatment i s only f e a s i b l e f o r s t r e t c h i n g v i b r a -  t i o n s i . e . above 550 c m  -1  as below 550 c m  great to allow unambiguous assignment.  -1  the number of bands i s too  85. IV  General Conclusions It was shown e a r l i e r that the number of p o s i t i v e halogen compounds  a v a i l a b l e obtainable from any oxyacid depends somewhat upon the strength of the a c i d .  Trifluoromethanesulfonic a c i d has been found to be a very  strong a c i d , comparable to f l u o r o s u l f u r i c a c i d . number of I-SO^CF^ compounds have been obtained.  A reasonably large These d i s p l a y , with  one e x c e p t i o n , IOSO^CF^, s t r u c t u r a l s i m i l a r i t i e s to the analogous fluorosulfates. The structures proposed f o r these compounds, both SO^CF^ and SO^F, have been based, f o r the most part on the analyses of t h e i r vibrational spectra.  The complexity of the spectra f o r SO^CF^ com-  pounds i s due t o the near coincidence of the S - 0 and C-F s t r e t c h i n g region.  However, much information which i s unobtainable f o r the f l u o r o -  s u l f a t e s because of t h e i r r e a c t i v i t y with i n f r a r e d c e l l window material was obtained f o r the trifluoromethanesulfonates which are r e l a t i v e l y unreactive. F i n a l l y , here are a few suggestions f o r f u r t h e r study i n t h i s area. 1.  The s o l v o l y s i s of BrF^ i n HSO^CF^ might be studied f u r t h e r  with a view to obtaining B r ( S 0 C F ) . 3  3  However* the detonations r e -  3  corded f o r other attempts to form B r ( S 0 C F ) 3  2.  3  suggest extreme c a u t i o n .  3  The s o l v o l y s i s of C1F in HS0 CF may y i e l d C1S0 CF . 3  3  3  C1N0  3  3  i s known while BrN0 i s not. 3  3.  The s o l v o l y s i s of BrS0 F i n HS0 CF may y i e l d B r S 0 C F . 3  3  3  3  3  The  s o l v o l y s i s of 1(1) compounds r e s u l t i n the formation of iodine c a t i o n s I  3  +  and  compounds.  along with  There might be more success with bromine(I)  86. 4.  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