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The synthesis and structural studies of tin(IV) and organotin(V) sulfonates Yeats, Philip Allen 1973

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171  V?  THE SYNTHESIS AND STRUCTURAL STUDIES OF TIN(IV) AND ORGANOTIN(IV) SULFONATES  BY  PHILIP A YEATS B.Sc.  (Hons.), University of B r i t i s h Columbia, 1969  A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY i n the Department of CHEMISTRY  We accept this thesis as conforming to the required standard  THE UNIVERSITY OF BRITISH COLUMBIA July, 1973  In p r e s e n t i n g  t h i s t h e s i s i n p a r t i a l f u l f i l m e n t of the r e q u i r e m e n t s f o r  an advanced degree a t the U n i v e r s i t y of B r i t i s h Columbia, I agree t h a t the L i b r a r y s h a l l make i t f r e e l y  a v a i l a b l e f o r r e f e r e n c e and  I f u r t h e r agree t h a t p e r m i s s i o n f o r e x t e n s i v e f o r s c h o l a r l y purposes may by h i s r e p r e s e n t a t i v e s .  study.  copying of t h i s  be g r a n t e d by the Head of my  thesis  Department or  I t i s u n d e r s t o o d t h a t c o p y i n g or p u b l i c a t i o n  of t h i s t h e s i s f o r f i n a n c i a l g a i n s h a l l not be a l l o w e d w i t h o u t written permission.  Department The U n i v e r s i t y o f B r i t i s h Columbia Vancouver 8, Canada  my  - i iABSTRACT The systematic investigation of the s o l v o l y s i s of methyltin(IV) chlorides of the type (CH„) SnCl, , 1 < n < 4, i n strong monobasic 3 n 4-n protonic acids, i n p a r t i c u l a r HSO^F and HSO^CF^, has resulted i n the preparation of new trimethyltin(IV), dimethyltin(IV) and methylchlorotin(IV) sulfonates.  P r e f e r e n t i a l cleavage of Sn-Cl over Sn-C  bonds was noted r e s u l t i n g i n mono- or b i s u b s t i t u t i o n on t i n depending on the mole r a t i o of the reactants.  Additional methylchlorotin(IV)  fluorosulfates could be obtained by n o n - s t a t i s t i c a l ligand r e d i s t r i b u t i o n reactions with chloride and fluorosulfate exchange between suitable substrates, e.g.  (CH ) Sn(S0 F) 3  2  3  2  + (CH ) SnCl 3  2  •  2  Inorganic fluorosulfates C l S n ( S 0 F ) 2  3  2  2(CH ) ClSnS0 F 2  3  and B r S n ( S 0 F ) 2  3  2  were  obtained by s i m i l a r ligand scrambling of either SnCl^ or SnBr^ i n Sn(S0 F)^.  Sn(S0 F)^ was found to undergo complete SC> F-C1 exchange  3  3  3  with T i C l ^ resulting i n the formation of T i C l ^ g ( S 0 F ) which appears 3  3  to have rather unique tetradentate SC^F groups. of the Lewis acid Sn(S0 F) 3  4  Br(SC> F) 3  cations.  + 2  3  2-  2  S n C 1  6  +  3  and Br(SC" F) 3  3  + + s a l t s with C10„ , I<S0-F) and o  Nitrosonium and a l k a l i metal hexakisfluorosulfato-  stannates are obtained by the reaction  M  Complexation reactions  with CIC^SC^F, I(SC> F)  r e s u l t i n the formation of Sn(SO.F)^  2  3 S  2°6 2 F  M  2  S n ( S  °3  F )  6  - iii  -  The reactions of the Lewis acids AsF  c  and SbF_ with some of the halogen  fluorosulfates mentioned above i s also discussed.  119 Structural studies are based on v i b r a t i o n a l and  Sn Mossbauer  spectra with the l a t t e r providing proof of the i d e n t i t y of the methyl2chlorotin(IV) fluorosulfates and the Sn(SO^F)^ ion. 2Except for the Sn(S0„F), compounds, the t i n i s either hexaJ o coordinated or occasionally pentacoordinated with the sulfonate groups acting as bidentate bridging links between the t i n moieties.  Two  s t r u c t u r a l types emerge: the octahedral b i s f l u o r o s u l f a t e s XYSnCSO^F^ with X, Y = CH^,  Br, CI, and SO^F  i n trans octahedral positions and  the t r i g o n a l bipyramidal X2YSnS0.jF.  Successful correlations of isomer  s h i f t s vs. the sum of the Pauling e l e c t r o n e g a t i v i t i e s of X and Y or quadrupole s p l i t t i n g vs. the Taft a  for X and Y indicate i s o s t r u c t u r a l  compounds for the b i s f l u o r o s u l f a t e s . The monofluorosulfates allow no 2such correlations. In Sn(SO.F), monodentate SO F groups give r i s e J D -> to an octahedral environment for t i n and hence a zero quadrupole splitting.  - iv -  TABLE OF CONTENTS Page ABSTRACT  1  1  LIST OF TABLES  i  x  LIST OF FIGURES  x  i  i  ACKNOWLEDGEMENT  x  i  v  I.  INTRODUCTION  1  A.  General Remarks  1  B.  Stereochemistry  2  1.  Complexes  3  2.  Autocomplexation  4  (a)  Bridging ligands  4  (b)  Chelating ligands  6  (c)  Carboxylates  6  3. C.  D.  E.  and thiocarbamates  Clusters  8  Bonding  9  1.  General considerations  9  2.  Methyltin cations  11  3.  Fluorosulfates as anion  12  Fluorosulf ates  13  1.  Synthetic routes to fluorosulfates  13  2.  Structural studies on fluorosulfates  15  3.  Previous work on t i n fluorosulf ates  16  V i b r a t i o n a l Spectroscopy  17  1.  Tin-carbon  17  2.  Fluorosulf ates  17  3.  Other sulfonates  21  - v Page F.  G.  II.  Mossbauer Spectroscopy  23  1.  Principles  24  2.  Isomer s h i f t  26  3.  Quadrupole s p l i t t i n g  28  4.  Room temperature effect  29  HSO^F as a Nonaqueous Solvent  30  EXPERIMENTAL  34  A.  Apparatus  34  1.  Drybox  34  2.  Vacuum l i n e s  34  3.  Reaction vessels  35  (a)  Glass  35  (b)  Metal  38  4.  Fluorosulfuric acid  38  5.  Conductometry  38  6.  Vibrational spectroscopy  39  7.  Mossbauer spectroscopy  40  8.  Nuclear magnetic resonance spectroscopy  40  9.  Melting points  41  Analyses  41  10. B.  C.  Chemicals  41  1.  Commercial sources  41  2.  Literature preparations  41  Suppliers of Materials and Equipment  44  - vi Page III.  METHYLTIN SULFONATES  46  A.  Introduction  46  1.  Previous work  46  2.  Promising routes to sulfonates  47  (a)  Solvolysis  47  (b)  Ligand r e d i s t r i b u t i o n  48  B.  C.  Preparations  49  1.  (CH ) Sn(S0 X)  2.  (CH > Sn derivatives of oxyacids  52  3.  CH ClSn(S0 X)  52  4.  (CH ) SnS0 X  5.  (CH ) ClSnS0 F and CH^Cl^nSC^F  6.  (CH ) Sn(S0 F)(S0 CF )  58  7.  CH Sn(S0 F)  58  3  3  2  3  2  3  3  3  3  3  49  2  3  2  54  3  2  3  2  3  3  3  3  3  3  Structural Studies  57  59  1.  (CH ) Sn(S0 F)  2.  Other methyltin sulfonates  67  (a)  (CH ) Sn(S0 X)  67  (b)  (CH ) SnS0 X  (c)  CH ClSn(S0 X) , CH^Cl^nSO^ and  3  2  3  3  3  59  2  2  3  3  3  70  3  3  2  2  3  2  (CH ) ClSnS0 F D.  .-  3  77  Discussion  79  1.  Syntheses  79  2.  Spectra  82  3.  Bonding  87  - vii-  Page IV.  INORGANIC TIN FLUOROSULFATES  95  A.  Introduction  95  B.  Preparations  96  C.  D.  1.  Sn(S0 F)  2.  Cl Sn(S0 F)  3.  Cl SnS0 F  4.  Br Sn(S0 F)  2  96  4  3  3  97  2  99  3  2  3  100  2  Structural Studies  101  1.  Mo'ssbauer spectra  101  2.  V i b r a t i o n a l spectra  103  Reactions  of S n ( S 0 F ) 3  4  105  1.  Introduction  105  2.  Ligand r e d i s t r i b u t i o n reactions  106  (a)  GeCl. and S i C l . 4 4  106  (b)  TiCl  107  3.  V.  3  4  Complexation reactions (a)  NOCl  (b)  N0 F and C1F  (c)  Adduct formation  2  110 I l l  3  112 112  CORRELATIONS OF MOSSBAUER PARAMETERS FOR TIN FLUOROSULFATES  114  A.  Correlations f o r T i n Fluorosulf ates  114  B.  Other Possible Correlations  119  C.  Point Charge Model  120  - viii -  Page  VI.  VII.  THE HEXAKISFLUOROSULFATO STANNATE(IV) ION  123  A.  Introduction  123  B.  Preparations  124  1.  (C10 ) Sn(S0 F)  2.  [Br(S0 F) ] Sn(S0 F)  3.  [I(S0 F) ] Sn(S0 F)  4.  K Sn(S0 F) , Cs Sn(S0 F)  2  2  3  3  2  3  2  2  3  124  6  2  3  2  3  6  125  6  126  6  2  3  6  and  (NO) Sn(S0 F) 2  3  g  .  126  C.  Mossbauer Spectra  129  D.  V i b r a t i o n a l Spectra  132  E.  Solution Studies i n HS0 F 3  142  REACTIONS OF LEWIS ACIDS WITH FLUOROSULFATES  147  A.  Introduction  147  B.  C10 S0 F Reactions  148  1.  C10„S0_F + SnF. 2 3 4  148  2.  C10 S0 F + SbF  5  148  3.  C10 S0 F + AsF  5  153  4.  C10 S0 F + BF  2  3  2  2  2  3  3  3  155  3  C.  KS0 F + SbF  D.  BrS0 F and Br(S0 F) . Reactions  3  156  5  3  3  3  VIII. GENERAL CONCLUSIONS  157 159  A.  Summary  159  B.  Suggestions f o r Further Work  161  REFERENCES  163  - ix -  LIST OF TABLES Table  Page  1  Methyltln Halides  9  2  Conformations  3  Methyltin Vibrations  4  S-0 Stretching Frequencies f o r Monodentate SO^F  ...  19  5  Stretching Frequencies for B i - and Tridentate S0 F.  22  6  Previous Assignments f o r SO^CF^  22  7  Trimethyltin Carboxylates  31  8  Physical Properties of HS0 F  31  9  Chemicals  42  10  Dimethyltin Sulfonates - Analyses  51  11  Elemental Analyses of ( C H ^ S n Salts  53  12  Other Methyltin Sulfonates - Analyses  55  13  Reported Interatomic Distances and Selected Bond  of Fluorosulfates  19 19  3  3  Angles for some Fluorosulfates  ..  14  V i b r a t i o n a l Spectra of ( C H ) S n ( S 0 F )  15  E l e c t r i c a l Conductivity of (CH > Sn(S0 F)  3  2  3  3  2  61 63  2  3  2  i n HS0 F 3  at 25°  66  16  Mossbauer Data for ( C H ) S n ( S 0 X )  17  V i b r a t i o n a l Frequencies of (CH > Sn(S0 X)  18  Dimethyltin Derivatives of Oxyacids - Spectral Results  69  19  V i b r a t i o n a l Frequencies for ( C H ^ S n S O ^  71  3  2  3  3  2  66  2  3  2  Compounds  68  119 20  Sn Mossbauer Data f o r (CH ) Sn(IV) Compounds 3  at 80°K  3  74  - x Table 21  Page S p e c i f i c Conductance of (CH^SnSC^F and (CH ) Sn(S0 F) 3  22  2  3  75  2  V i b r a t i o n a l Spectra of (CH.) CI Sn(SO.X). 3 x y 3 4-x-y Mossbauer Data for (CH„) CI Sn(S0 X). 3 x y 3 4-x-y Preparative Routes to (CH„) CI Sn(SO„F), 3 x y 3 4-x-y  78  r  23 24  79  o  80  r  25  Vibrational Modes of the S0 F Group i n Various Tin 3  and Methyltin Fluorosulfates 26  84  Tin-carbon and Tin-chlorine Stretching Modes i n the Methyltin(IV) Chloro-sulfonate Compounds  85  27  A n a l y t i c a l Results f o r Inorganic T i n Fluorosulfates  98  28  Mossbauer Parameters f o r Inorganic T i n Fluorosulfates  102  29  V i b r a t i o n a l Spectra of Inorganic T i n Fluorosulfates  102  30  Vibrational Spectra of T i C l  31  Point Charge Predictions f o r some Methyltin(IV)  3  1 ( )  Compounds 32 33  3  2  2  2-  109  122 128 130  V i b r a t i o n a l Spectra of A l k a l i Metal Hexakisfluoro133  V i b r a t i o n a l Spectra of Heterocation Hexakisfluorosulf atostannates (IV)  36  2  b  sulf atostannates(IV) 35  3  A n a l y t i c a l Results f o r Sn(S0„F), Compounds o o 2Mossbauer Spectra of Sn(S0„F),. Compounds at 80°K. 3  34  ( S 0 F ) and T i C l ( S 0 F >  134  V i b r a t i o n a l Spectra of Halogen Bisfluorosulfates Hexakisfluorosulfatostannates(IV)  135  37  Br(S0 F)  139  38  L i t e r a t u r e Values for vBr-0 and vBr-F  3  + 2  V i b r a t i o n a l Modes  141  - xi -  Table  Page  39  Br-0 Stretches i n Fluorosulfates  141  40  E l e c t r i c a l Conductance of K Sn(S0_F) and o  c  2.  3 D  (C10 ) Sn(S0„F) , i n HSO.F at 2 5 ; y V a l u e s 0  o  II  o  3  b  143  3  41  V i b r a t i o n a l Spectra of CIO Sb F  42  Vibrational Spectra of Sb„F  150  2  i  ~ and SbF ~ Salts  11  151  o  43  Raman Spectrum of ClC^AsF^C^F  154  44  Raman Spectrum of Br(S0 F) SbF  158  - xii -  LIST OF FIGURES Figure  Rage  1  Structures  of Dimethyltin(IV) Fluoride and Chloride  2  Structural Features of some Organotin(IV)  5  o  Carboxylates and Dithiocarbamates, Bond Distances i n A  7  3  Correlation Diagram for S0 F  20  4  Decay of ^ g S n ^ ^  25  5  Isomer S h i f t , 6 (mm/sec)  25  6  D i s t r i b u t i o n of 6 for Sn(IV)  27  7  Quadrupole Coupling A (mm/sec)  27  8  Reactors  37  9  The Crystal Structure  10  3  m  of ( C H ) S n ( S 0 F )  E l e c t r i c a l Conductivity  3  2  3  of ( C H ) S n ( S 0 F ) 3  2  60  2  3  2  in  HS0 F at 25° iiq  65  3  11  Sn Mossbauer Spectrum of (CH ) SnS0 CH 3  3  3  3  at 80°K.  12  Specific Conductivities  i n HS0 F at 25.0°C  13  Comparison of Mossbauer Parameters of Dialkyltin(IV)  74 76  3  Difluorides Bisdifluorophosphates, Bisfluorosulfates and Bistrifluoromethylsulfonates  83  14  Structural Features of ( C H ) S n ( S 0 F )  15  pTr-dTr Bonding i n Fluorosulf ates  16  S-0  17  Structural Features of Trimethyltin f l u o r o s u l f a t e . .  18  Correlation Between Isomer Shifts and  3  2  3  88  2  90  Bond Lengths and TT Bond Orders  90  Pauling  E l e c t r o n e g a t i v i t i e s of the Ligands X i n the X Sn(S0 F) 2  3  2  92  Series 117  - xiii -  Figure 19  Page Correlation Between Taft's Inductive Constants and Quadrupole S p l i t t i n g i n the Series X Sn(S0 F> 2  X SnF 2  3  2  and 118  2  20  Raman Spectrum of [ B r ( S 0 F ) ] S n ( S 0 F )  21  Conductivities of K„Sn(S0„F)  3  2  2  r  3  6  and (CIO^) Sn(S0 F) .  136 144  xiv  ACKNOWLEDGEMENTS I am very grateful to Dr. F. Aubke for suggesting this topic and for his constant encouragement and advice during the course of this work.  I would also l i k e to thank Dr. J.R. Sams for help with respect  to the MSssbauer spectra and Mrs. A. Sallos for technical assistance with these spectra. The work of Messers. S. Rak and J . Molnar of the glass blowing shop i s appreciated.  I would also l i k e to thank Ms. Diane Johnson  for typing the thesis. I am also grateful for a MacMillan Family Foundation Fellowship awarded to me from 1971-1973.  - 1 -  CHAPTER I INTRODUCTION  A.  General Remarks In recent years there has been an increasing interest i n the  chemistry of t i n . factors.  This increase can be a t t r i b u t e d to several  These include:  1) the a b i l i t y of t i n to form bonds with  almost a l l the elements, p a r t i c u l a r l y the f a i r l y stable bonds formed with the more abundant elements oxygen, nitrogen, carbon, hydrogen, and the halogens, to produce an extraordinary wealth of t i n organotin compounds;  and  2) the a p p l i c a b i l i t y of an unusually wide  range of preparative routes to the synthesis of t i n and  organotin 119  compounds;  3) the advent of physical techniques  to a lesser extent ^^Sn  such as  Sn and  nuclear magnetic resonance spectroscopies  119 and  Sn Mossbauer spectroscopy;  4) the fact that t i n and  compounds are readily available and not overly expensive;  organotin as well as  5) the possible i n d u s t r i a l a p p l i c a t i o n of a wide variety of t i n compounds.  The increased interest i n the area of organotin  chemistry  i n p a r t i c u l a r i s best documented by a number of books on the subject 12 3 which have appeared . recently i n f a i r l y short succession. ' '  2 The fact that a data c o l A ^ - i o n on organotin compounds compiled i n 1967^ must now be considered as outdated and the number of papers which have appeared since che work was  started on the s p e c i f i c area  with which this thesis i s concerned are i n d i c a t i v e of the interest. As i s apparent from the more recent review a r t i c l e s on organotin chemistry the main i n t e r e s t i n the chemistry of t i n centers around three important problems.  These are the stereochemistry and structure  5 6 6 of t i n compounds ' as deduced from X-ray d i f f r a c t i o n studies, Mossbauer studies,^'^'^ v i b r a t i o n a l spectroscopy,^ and nuclear magnetic resonance spectroscopy,^ the bonding between the t i n atom . . ... 5,11,12 . . . „. . 13,14 and i t s neighbours, and the r e a c t i v i t y of t i n compounds. Almost a l l of this interest i s centered around compounds of t e t r a valent t i n . Compounds of divalent t i n , especially organometallic derivatives, have received r e l a t i v e l y l i t t l e attention,''""' perhaps with the exception of SviF^ which i s widely used i n f i g h t i n g tooth decay and has been the subject of many c l i n i c a l studies."^ The general references, monographs, reviews, and data c o l l e c t i o n s mentioned above are a l l useful sources for information on the various aspects outlined here.  A number of i n d i v i d u a l topics relevant to the  intention and scope of t h i s study w i l l be discussed i n greater d e t a i l i n the following sections.  B.  Stereochemistry A f a i r l y wide variety of coordination numbers and geometries have  been observed  f o r compounds of tetravalent t i n . The coordination  numbers range from four i n simple tetrahedral molecules such as  - 3-  tetramethyltin or t i n tetrachloride to the more common f i v e or s i x and the rarer seven or even eight coordination.  Higher coordination  can be achieved i n three general ways and some reported structures are given as examples of each type.  1.  Complexes The coordination number can be expanded to f i v e or s i x by  complexation with neutral molecules, L, to form molecular complexes or adducts, or with anions, X , to form anionic complexes:  SnX,  + nL  SnX,  + nX  SnX.(L) 4 n  [ S n X  (W  n-  An example of a pentacoordinated adduct i s the t r i g o n a l bipyramidal (CH^^SnCl.py''"^ i n which the three methyl groups occupy the three 18 equatorial positions i n the bipyramid.  SnCl^.2SeOCl2  and  19 SnCl «2py  are both examples of hexacoordinated  4  the stereochemistry at t i n i s octahedral.  adducts i n which  The selenium oxychloride  adduct has the two SeOC^ molecules c i s to one another and the pyridine adduct the pyridines are trans.  In a l l instances of SnCl^ adducts  either the more common c i s , or the trans adducts are formed, but never both isomers f o r one ligand. tin  Anionic complexes i n which the  i s either f i v e or s i x coordinate are also known. 3-Chloro-l,2,3,420 tetraphenylcyclobutenium pentachlorostannate has a t r i g o n a l bipyram21 i d a l . SnCl anion and sodium hexafluorostannate an octahedral c  - 4 SnF g  2-  anion.  Studies on mixed anion complexes, e.g.  SnCl^Br^  2-  22  23 are also reported.  Cs^(CH^)^SnCl^  i s an example of an anionic  organotin complex shown by infrared results to have trans methyl 2groups i n an octahedral  2.  (CH^^SnCl^,  anion.  Autocomplexation The coordination number of t i n can also be expanded by auto-  complexation. such as NO^  In autocomplexation a nominally monodentate ligand or F  i s involved i n further coordination, either 2-  bridging or chelating.  Bidentate ligands such as SO^  autocomplex by acting as t r i - or tetradentate (a)  Bridging  can also  ligands.  ligands  Examples of hexacoordinated structures with bridging ligands are found f o r S n F , 4  2 4  (CH^SnF^  2 5  and  (CH^SnCl^  2 6  Both fluorides  form sheetlike polymers with f l u o r i n e bridges, and i n each case the bridging t i n - f l u o r i n e distances are both equal. methyl groups i n (CH )2SnF 3  2  As shown i n Figure  1,  occupy trans positions i n the octahedron  with l i n e a r CH.-Sn-CH„ r e s u l t i n g i n D,, symmetry (I4/mmm for the J j 4n crystal).  (CH^^SnC^, on the other hand, has a distorted tetrahedral o  environment around t i n with weak chlorine bridges, unequal (1.1 A difference) t i n - c h l o r i n e bond lengths, and an angular CH^-Sn-CH^ grouping.  These two compounds i l l u s t r a t e the two possible extremes  i n the extent of autocomplexation.  - 5 -  Figure 1. Structures of Dimethyltin (iv) Fluoride and Chloride  ( C H ^ SnCl  2  Trigonal bipyramidal complexes with bridging ligands are also known.  The most common examples of this type of coordination are  t r i a l k y l t i n compounds such as (CH^SnNCS,  27  (CH^SnCN,  28  or  29 (CH^^SnF,  which have planar (CH^^Sn moieties joined  by bidentate NCS,  together  CN or F bridges to form c h a i n - l i k e polymers.  Trimethyltin isothiocyanate i s d e f i n i t e l y an isothiocyanate, i . e . i t has a short tin-nitrogen bond and a r e l a t i v e l y longer bond.  tin-sulfur  In t r i m e t h y l t i n cyanide, on the other hand, the CN group i s  found equidistant from the two neighbouring  t i n atoms.  Trimethyltin  f l u o r i d e , an example of f i v e coordinate structure with a single atom bridge, has a disordered structure with two possible solutions.  In  -6 both p o s s i b i l i t i e s the t i n - f l u o r i n e - t i n grouping i s non-linear and the two t i n - f l u o r i n e bond lengths are unequal.  (b)  Chelating ligands  Some examples of complexes with chelating ligands are dimethyltin bis 8-hydroxyquinolinate,  30  methyltintrinitrate,  31  and t i n t e t r a -  32 nitrate.  (CH^^SnCCgHgNO^ i s s i x coordinate with the nitrogen and  oxygen atoms of each 8-hydroxyquinolate  occupying adjacent positions  on the octahedron around t i n . The methyl groups are also c i s . In methyltin t r i n i t r a t e the t i n atom i s seven coordinate with three bidentate chelating n i t r a t e groups and one methyl group and i n t i n t e t r a n i t r a t e the eight oxygen atoms of the four bidentate chelating n i t r a t e groups form a s l i g h t l y distorted dodecahedron around the t i n atom. (c)  Carboxylates and  thiocarbamates  Triorganotin carboxylates and thiocarbamates form an interesting i l l u s t r a t i o n of the possible v a r i a t i o n s i n t i n coordination because these two closely related anions form both tetrahedral and bipyramidal structures.  trigonal  Examples of these d i f f e r e n t stereochemistries 33  are shown i n Figure 2.  T r i b e n z y l t i n acetate  has a f i v e coordinate  t r i g o n a l bipyramidal structure with three benzyl groups equatorial 34 and the bridging acetates a x i a l .  T r i c y c l o h e x y l t i n acetate,  however, has a distorted tetrahedral structure with a monodentate acetate group.  The difference i n coordination i s attributed to the  increased s t e r i c hindrance of the cyclohexyl groups.  Similar changes  - 7 -  Figure  2  Structural Features of Some Organotin (iv)-Carboxytates o  and Dithiocarbamates,Bond Distances in A. a)  0 R 14 Sn—OlTj, I ?  O  v  2 65 >VO-"~'""Sn  R, Sn.' R  R.  C  s<  R  R= B e n z y l  R= Methyl ^ O  b)  C  Sn R  «J.^-. 5o  2.95  „ Sn  d) R—pSn^  R  R = Cyclohe>cyl  R = Methyl  J\>  N  - 8 -  from f i v e to four coordination observed when the size of the substituent on the 3 carbon of the carboxylate i s increased are also 35 attributed to s t e r i c hindrance.  The  N,N-dimethyl-dithiocarbamate  derivatives also exhibit both tetrahedral structures and a pentacoordinated structure, the l a t t e r with a chelating dithiocarbamate 36 group. Trimethyltin N,N-dimethylf.dithiocarbamate occurs i n three d i f f e r e n t c r y s t a l forms a l l of which have a distorted tetrahedral arrangement about the t i n atom £nd dimethylchlorotin N,N-dimethyl37 dithiocarbamate  i n a distorted t r i g o n a l bipyramidal structure with  two methyl groups and one sulfur i n the plane and the chlorine and second sulfur atom a x i a l .  The change i n coordination i s presumably  caused by the increased acceptor strength of the t i n atom i n the ( C H ^ C l S n derivative. 3.  Clusters A t h i r d d i s t i n c t type of compound which contains t i n with an  expanded coordination number i s cluster compounds i n which t i n i s bonded to either t r a n s i t i o n metals or other elements.  An example of a  t r a n s i t i o n metal cluster with six-coordinated t i n atoms i s (C H ) Pt„(SnCl_) . o 1/ 3 3 5 2. 0  38  The structure which has been proposed for the 39  carborane l-stanna-2,3-dicarba- closo- dodecaborane (11), has a pentacoordinate t i n at the apex of an icosahedron.  BgC^SnH.^,  -  9  C.  Bonding  1.  General considerations  -  The electron configuration f o r the ground state of t i n i s 10  2 2 5s 5p and the corresponding valence state would be 10 3 3 [Kr]4d 5s5p . This suggests sp hydridization f o r compounds of the [Kr]4d  R^Sn  type.  A rehydridization of the t i n valence o r b i t a l s resulting i n  greater s electron density i n o r b i t a l s involved i n bonding to carbon w i l l occur i n substituted organotin compounds with substituents more 40 electronegative than carbon.  Evidence for this change i s found i n the 1 119 higher tin-carbon stretching frequencies, larger HSn nmr coupling 41 42 119 constants ' and the larger Sn Mossbauer isomer s h i f t s for compounds with more electronegative ligands. i l l u s t r a t e d i n Table 1.  These trends are  Tin-carbon bond lengths should also decrease  Table 1.  Compound  v  (CH ) Sn 3  4  (CH ) SnCl 3  3  (CH ) SnCl 3  2  CH SnCl 3  2  Sn-C  s  Sn-C 43  v  avg  Sn-C  a  <5 (mm/sec)^  %119 n S  44  41 53. 8*  545  45  514  45  535  1.43  46  58.5  41  563  45  524  45  544  1.54  26  69.7  41  99.5  41  '508  598  46  J  45  520  1.29  548 532  46  576  Calculated according to Lehman's Rule. Mossbauer isomer s h i f t r e l a t i v e to Sn0 . 2  Nmr  J  43  548 2  v  ^524  3  (CH ) SnF 3  2  a  spectra recorded i n CC1. solution at 31°.  C  - 10 -  but unfortunately i n s u f f i c i e n t r e l i a b l e data are available to indicate any trends.  The observed tin-carbon bond lengths are i n the f a i r l y o  wide range of 2.08  to  ^2.21  A.  This trend to higher s character around t i n i s most obvious for the octahedrally coordinated dimethyltin d i f l u o r i d e which has  the  o  shortest tin-carbon bond length (2.08 A) and the highest value of the 3 2 halides for vSn-C. on t i n would suggest  A s i m p l i s t i c view of bonding using sp d ^17% s character and correspondingly  bonds and a decrease i n isomer s h i f t .  orbitals longer  These expectations are not  confirmed by experiment. Two views can be quoted to explain the experimental  observations. 2+ (1) (CH.j)2SnF2 can be regarded as an i o n i c s o l i d with (CH^^Sn and F ions and the bonding i n the C-Sn-C skeleton can be described 25 3 2 using an sp o r b i t a l on t i n . (2) Rehybridization of the t i n sp d 40 polyhedron according to Bent  whereby bonding to the least e l e c t r o -  negative ligands has a l l the s electron density, i . e . 2 2 for bonding to carbon, and the SnF^ segment has p d  ^sp o r b i t a l s  character has been  48 suggested.  The o v e r a l l structure of (CI^^SnF,^ i s better described  as polymeric with fluorine bridges than as i o n i c .  This view i s supported  by comparison to chain-like R^SnY compounds where Y i s a bridging group (C0 CH , CN, F, e t c . ) , by the p h y s i c a l properties (high melting 2  3  point, i n s o l u b i l i t y even i n i o n i z i n g solvents, n o n v o l a t i l i t y ) , by the occurrence  of the Mossbauer e f f e c t at room temperature, and by  the v i b r a t i o n a l spectrum.  V i b r a t i o n a l spectroscopy  i s particularly  useful f o r studies of s i m i l a r compounds with anions or anionic groups of p o t e n t i a l l y high symmetry, e.g. CIO.  .  - 11 -  2.  Methyltin cations The question of whether or not organotin cations, s p e c i f i c a l l y  2+ R^Sn  + and R^Sn , may exist now becomes interesting and two general  routes appear suited to this investigation. solids of formula R SnX 2  2  These are the study of  and R^SnX with R an a l k y l group, preferably  methyl to eliminate electronic repulsions, and X i s a monobasic anion of a very strong acid and the study of R,,SnX and R^SnX and other 2  suitable solutes i n strongly ionizing solvents such as protonic acids. The previous views on organotin cations are expressed i n review a r t i c l e s by R.S. Tobias  11  12  and H.C. Clark.  Tobias reviewed evidence f o r the existence of organotin cations i n aqueous solution obtained by measuring the equilibrium constants f o r hydrolysis and s t a b i l i t y constants f o r complexes of the cations with organic ligands as well as determinations of the structures of the solvated cations.  Using v i b r a t i o n a l spectroscopy, p a r t i c u l a r l y Raman  2+ r e s u l t s , the aquated (CH.j) Sn 2  cation was shown to be octahedral with  l i n e a r C-Sn-C skeleton and four water molecules  coordinated i n the  equatorial plane, and the (CH^^Sn" " cation t r i g o n a l bipyramidal with 1  planar equatorial (CH^^Sn group and two a x i a l water molecules.  Nmr  measurements indicated there i s a high degree of metal s character i n the metal-carbon bonds of the solvated cations, and that the metal solvent bonds are highly polar. Tobias then suggests on the basis of the stereochemistry i n the c r y s t a l l i n e state that the bonding i n the c r y s t a l i s also i o n i c with 2H~ ~l" 2 3 a bonded (CH^^Sn and (CH^^Sn cations using sp and sp hybrids respectively, joined to the anions by highly polar three center bonds using p o r b i t a l s on t i n . The extent of covalent i n t e r a c t i o n i n these  - 12 -  tin-anion bonds i s considered to be small and observed s p l i t t i n g of degenerate v i b r a t i o n a l modes i s thought to be due to s i t e symmetry effects. H.C.  Clark suggest on the basis of crystallographic and v i b r a t i o n a l  data that the extent of covalent bonding i n the s o l i d state i s much greater than suggested by Tobias. view are:  The main points supporting  this  (1) the Sn-F...Sn bridges i n (CH^^SnF are nonlinear,  (2) s p l i t t i n g s of degenerate infrared bands are too large for s i t e symmetry effects and are also observed i n methanol solutions of (CH^SnClO^,-and (3) the s p l i t t i n g s for (CH^SnCrO^ are larger by an order of magnitude than those of (NH^^CrO^.  In general, true  i n t e r a c t i o n between anionic and cationic groups i s found for a whole range of anions.  3.  Fluorosulfate as anion The anion group of choice i s the f l u o r o s u l f a t e group for the  following reasons.  (1) HSO^F i s one of the strongest simple monobasic  acids known and extensive work i n the HSO^F solvent system has been  49 done.  (2) Infrared and Raman spectra of the f l u o r o s u l f a t e anion  are known and indicate that the ion has C ^  symmetry.  Bridging or  chelation using two oxygens w i l l r e s u l t i n a symmetry reduction to C , causing p o s i t i o n a l changes as well as changes i n the number of s bands.  (3) A v a r i e t y of suitable preparative techniques  a s u f f i c i e n t l y large number of derivatives.  should provide  This variety i s i n con- =  trast to the s i t u a t i o n i n R^SnX compounds such as  hexafluoroantimonates  or arsenates"^ where only a few related derivatives are known.  - 13 (4)  Extension of the study to other related molecules should  informative.  be  The related acid groups -SC^CF^ -SC^Cl and -S0 CH 3  provide an easy means of a l t e r i n g the n u c l e o p h i l i c i t y of the group.  Extension and comparison to the i s o e l e c t r o n i c ClO^  3  SC^X or  ^2^2  ions should also be possible i n addition to synthesis of purely inorganic tin(IV) fluorosulfates^"'' using other preparative routes. (5)  In contrast to the perchlorate derivatives which were found to 52  be explosive, (6)  the SC^X  derivatives should be safe to handle.  Like the i s o e l e c t r o n i c ClO^ , SC>F 3  i s a poor coordinating ligand.  This fact should preclude any extensive complexation such as formation of [Me„Sn(SO„F) ] ^ ^ hen HSO„F i s used as a fluorosulfonating agent. 3 3 n 3 n _ 1  w  Some disadvantages of f l u o r o s u l f a t e s w i l l have to be kept i n mind.  The S-F bond i s sensitive to hydrolysis.  This i s a pH  dependent process, e.g. KS0 F can be r e c r y s t a l l i z e d from water but i s 3  hydrolyzed  rapidly i n a c i d i c or basic solution.  As a consequence  water would not be a suitable solvent for i o n i z a t i o n studies. the f l u o r o s u l f a t e group i s thermally l a b i l e .  Two  cleavage are elimination of SC> and elimination of 3  Also,  common modes of S  2°5 2' F  S  °2 2 ° F  r  other p o l y s u l f u r y l f l u o r i d e s .  D.  Fluorosulfates  1.  Synthetic routes to fluorosulfates The chemistry  of f l u o r o s u l f a t e s has been f a i r l y extensively  studied and their preparation, properties and reactions have been 49 53-55 reviewed recently.  '  The chemistry  of the f l u o r o s u l f a t e group  i s i n many ways s i m i l a r to that of the halogens and i s found to meet  - 14 a l l but one of the requirements  established by Cotton and  56 Wilkinson  f o r a pseudohalogen.  Fluorosulfates are usually prepared by one of three methods 57-59 (1)  i n s e r t i o n of SO^ into an element-fluorine bond,  such as the reaction of calcium f l u o r i d e with SO^ at 200° to produce 58 calcium b i s f l u o r o s u l f a t e 200° CaF  (2)  +  2  2S0  »  3  Ca(S0 F) 3  2  reaction of f l u o r o s u l f u r i c acid with metal f l u o r i d e s ,  chlorides or c a r b o x y l a t e s , ' ^ e.g.  ZnCl  and  (3)  +  2  HS0 F  »  3  Zn(S0 F) 3  +  2  2HC1  reaction of substrates such as chlorides, bromides, oxides  or even the elements with the fluorosulfonating agents peroxydisulfuryl dif l u o r i d e , S - C K F - , 2  fluorosulfate.  HgO  6  bromine f l u o r o s u l f ate, ^  or chlorine  2  Examples of reactions of the t h i r d type are  +  SiCl. 4  2S 0 F 2  +  6  2  -  2BrS0_F 3  Hg(S0 F) 3  »-  2  +  0  SiCl (S0 F)_ 2 3 2 o  Reaction with the p o t e n t i a l l y oxidizing S 0gF 2  o  2  +  2  +  6 1  2BrCl  6 2  or BrS0 F may 3  not be  suitable for synthesis of organotin fluorosulfates because of oxidation of the organyl group.  Another rather general preparative  - 15 method commonly used to synthesize oxyacid derivatives - the s a l t method - i s not applicable  to the synthesis of  because AgSO^F i s d i f f i c u l t to  2.  Structural studies on  silver  fluorosulfates  obtain.  fluorosulfates  Structural studies have been reported for compounds containing both i o n i c and  covalently bonded f l u o r o s u l f a t e s .  found for a l k a l i , * '  3  alkaline earth ^ and 6<  Ionic bonding i s  some other metal f l u o r o s u l f a t e s ^ 6<  as well as for fluorosulfates of some heterocations such as N0 + 64 NC>2 .  or  +  The  c r y s t a l structures have been determined for two of these 65 66 s a l t s , KS0 F and NH,SO„F. A c r y s t a l structure has also been 3 4 3 67 o  reported for acetate acidium f l u o r o s u l f a t e ,  CH^C(OH)^SO^F.  In this  case the fluorosulf ate ion i s hydrogen bonded to the CHgCKOH^" " cation 1  r e s u l t i n g i n bidentate fluorosulfate groups. Mostly v i b r a t i o n a l spectroscopy has been used to study bonded f l u o r o s u l f a t e s .  S„0,F ,  and FSO.F L D 2. J J 3 were a l l shown by Raman spectroscopy to be covalently bonded with monodentate fluorosulfate groups. Two examples of bidentate covalent 6 8 , 6 9  o  f l u o r o s u l f ates have been reported.  BrS0„F,  70  C1S0„F,  covalently  SbF^SO^F''^ was  69  6 9  shown primarily  by  19 F nmr  measurements to have fluorosulfate bridging, however, no  v i b r a t i o n a l assignment i s made and  the infrared and Raman spectra  that are reported d i f f e r substantially.  More recently a report  on  72 SeF^SO^F and nmr  indicates bidentate SO^F spectra.  groups on the basis of v i b r a t i o n a l  Tridentate fluorosulfates are also possible  and 73  one  example of such a conformation has been found i n Co(S0.jF)2  quite  recently.  - 16 -  3.  Previous work on t i n fluorosulfates There are two reports of synthesis of inorganic tin(IV) fluoro-  sulfates i n the l i t e r a t u r e .  Hayek et a l . reported  the reaction of  SnCl^ with HSO^F to produce a mixed product most l i k e l y made up of 59 Cl Sn(S0 F) 2  3  and C l S n ( S 0 F ) ,  2  3  and Lustig and Cady reported the  3  reaction of SnCl, with S~0,F_ to produce ClSn(SO_F),. 4  z o 2  Sn(SO_F).  51  3 3  3 2  74 has also been prepared.  While some of this work i s of a preliminary  nature and not even v i b r a t i o n a l spectra are reported, indicate that t i n fluorosulfates may be thermally  i t does  stable and not  spontaneously decomposed to f l u o r i d e s , oxides or sulfates as i s found, e.g.  for s i l i c o n fluorosulfate d e r i v a t i v e s . ^  76 Trimethyltin f l u o r o s u l f a t e has been reported as well as several organotin derivatives of other sulfonic acids. These include (CH ) SnS0 CF , 3  3  3  77  3  (CH ) S n ( S 0 C F ) , 2  3  3  2  7 7  (CH > SnSC> CH , and 78  3  3  3  3  79 (CH ) Sn(SC> CH ) . 3  2  3  3  Only replacement reactions with the acids or  2  the s i l v e r s a l t method appear to be applicable to the synthesis of methyl-, trifluoromethyl-, or chlorosulfates as well as to the i s o e l e c t r o n i c difluorophosphates. used on occasion, (CH ) SnS0 CH . 3  3  3  3  to y i e l d  78  3  3  3  3  e.g. i n the reaction of S0 with (CH )^Sn,  (CH ) Sn  S0  Insertion of S0 has also been  +  4  S0  3  (CH ) SnS0 CH 3  3  3  3  i n s e r t i o n has also been used i n the reaction with SnCl^ presumably  to produce SnCl (S0 C1) 2  3  2  80  - 17 -  E.  V i b r a t i o n a l Spectroscopy In the study of the v i b r a t i o n a l spectra of t i n and organotin  fluorosulfates attention can be focussed on two main points; the tin-carbon stretching vibrations i n the 620-500 cm  1  range and the  fluorosulfate anion stretching vibrations which are expected i n the range of 1500-700 cm" . 1  1.  Tin-carbon If we take the compound (CH^^SnSO^F as an example, there w i l l  be two possible conformations for the C^Sn moiety, i t can be either planar or pyramidal.  S i m i l a r l y for (CH^^Sn compounds the p o s s i b i l i t i e s  are a l i n e a r or a nonlinear C^Sn grouping. with a planar C^Sn group i s (CH^^SnF.  An example of a molecule  This molecule has  29 symmetry  and the infrared and Raman a c t i v i t i e s and i n t e n s i t i e s of  the asymmetric and symmetric Sn-C stretches  should be as follows:  v Sn-C, weak i n the Raman and strong i n the infrared, and v Sn-C, 3.  S  strong i n the Raman and inactive i n the infrared.  I f the C^Sn moiety  i s nonplanar the symmetry w i l l be C^ and both tin-carbon v  stretches  w i l l be active with comparable i n t e n s i t i e s i n both the infrared and Raman spectra. 2.  An example of this case would be (CH^^SnCl.  Fluorosulfates The  conformations for the f l u o r o s u l f a t e group include  p o s s i b i l i t i e s summarized i n Table 2.  The SO^F  ion has  the f i v e symmetry  and s i x v i b r a t i o n a l modes, a l l of which are active i n both the infrared and Raman spectra.  These modes can be described as asymmetric and  - 18 symmetric S0„ stretches, v SO„(E) and v SO„(A), S-F stretch, vS-F(A), 3 a 3 s 3 bends, 6  asymmetric and symmetric SO  cl  3  rocking mode T SO^F(E).  SO„(E) and 6 SO (A), and a J S J  If the fluorosulfate group i s coordinated  to  the t i n atom i n a monodentate or bidentate manner, i t s symmetry w i l l be lowered to C  g  r e s u l t i n g i n an increase i n the t o t a l number of  modes due to SO^F.  The coordination over 0 (or F) should also reduce  the electron density i n the S-0  (or S-F)  bonding region which i n turn  w i l l increase the back donation from the remaining terminally bonded atoms and therefore cause changes i n the positions of the v i b r a t i o n a l modes. The following diagnostic c r i t e r i a should emerge f o r d i s t i n c t i o n between the four covalent (1)  possibilities.  The t o t a l number of SO^F  vibrations should allow d i s t i n c t i o n  between monodentate and bidentate on one hand and other possible conformations. (2)  An increase i n the energy of VS-F  the tridentate case and a decrease for the (3)  The positions of the SO^  would be expected for tetradentate.  stretching modes should be  d i f f e r e n t i n the monodentate case than they are i n the bidentate  case.  For a v i b r a t i o n a l analysis of this sort the following factors must be (1)  considered. The observed motions should be pure motions and not mixed. 81  This has been found to be the case for f l u o r o s u l f a t e s . (2)  The vibrations should be e a s i l y i d e n t i f i e d and not obscured.  For methyltin fluorosulfates the positions of the methyltin vibrations are well established and the positions of these bands as shown i n  - 19 TABLE 2 Conformations of Fluorosulfates Conformation  Description  Symmetry  S0 F  ionic  0*S02F  monodentate  0 *S0F  bidentate  c  tridentate tetradentate  5  2  0 *SF* 5  c  c  Ho. of modes ( a l l are i r and Raman active)  No. of stretching modes 3  6 (3A.5E)  3v  9  s  4  (6A',3A")  9 (6A',3A")  4  °3v  6 (3A,'3E)  3  °3v  6 (3A.3E)  3  s  i n d i c a t e s bidentate 0 or P 0, F i n d i c a t e s monodentate 0 or F  - TABLE 3 Methyl-tin Mode •v CH a  Vibrations  Position 3000  5  I r Intensity  cm"  1  VgCHj  2900  5 CH  3  1400  weak  S CH  5  1200  weak  800  strong  500-600  varied  a  S  CH-j rock . VSn-C  TABLE 4 S-0 Stretching Frequencies f o r Monodentate SO-^F Mode  Compound CISO^J? ^ BrSO-jF? S 0 F 6  0  2  ^ ( S0 ) 7  a  2  s 2) S 0  "^ ( SO) 2  1478CM"' 1438  6  1498  6 9 2  Xe(S0jF) 1425  8 2 2  HSOjF ? 8  1445  1 5  1206  1248  1238  1230  856  884  847  959  960  2 2  - 20 Table 3 should lead to only a minimum of overlap. (3)  The s p l i t t i n g or s h i f t i n g of v i b r a t i o n a l modes should be  caused by conformational differences or by weak anion-cation  and not by s i t e symmetry e f f e c t s  interactions.  Some examples are taken from the l i t e r a t u r e to i l l u s t r a t e these points.  The i o n i c f l u o r o s u l f a t e i s t y p i f i e d by KS0 F and the positions 3  of the s i x v i b r a t i o n a l modes of the S0 F anion i n KS0 F are shown i n 3  the c o r r e l a t i o n diagram, Figure 3.  3  An example of an i o n i c f l u o r o s u l f a t e  FIGURE 3 Correlation Diagram for SO3P c  3v 1285  C  ^  s  CISO3F  69  ?  OK"  1  ( A " ) ^i(A')  1478  1225  1079  745  \> W)  -fyA')  856  630  2  594  570  407  0 (A") ^ (A») ^ (A') ^ ( A " ) 6  4  534  4c6  3  9  573  which shows s p l i t t i n g of the E modes due to anion-cation  3o9  %{k')  363  interactions  64 or s i t e symmetry e f f e c t s i s N0S0 F.  In t h i s case the three E  3  modes are s p l i t by between 12 and 32 cm The best examples of monodentate f l u o r o s u l f a t e s are the halogen f l u o r o s u l f a t e s ^ ' ^ one of which, C1S0 F, i s shown as an example of a C symmetry f l u o r o s u l f a t e i n the c o r r e l a t i o n diagram. The biggest s 7  3  difference between the spectrum of C1S0 F and that of KS0 F i s that 3  3  C1S0 F has nine v i b r a t i o n a l modes compared to s i x f o r KS0 F. 3  3  The  s p l i t t i n g of these E symmetry modes, most obvious f o r v SO. i s much a J larger f o r C1S0 F than i t i s f o r N0S0 F. In addition the p o s i t i o n of 3  3  - 21 -  v S-F  i s s i g n i f i c a n t l y raised i n CISO^F.  change i n electron density  i n the S-0  number, the positions of the S-0  Because of the expected  region with change i n  coordination  stretching modes for monodentate  SO-jF, l i s t e d i n Table 4, are of i n t e r e s t . Very few v i b r a t i o n a l spectra of b i - or tridentate  fluorosulfates  and no examples of tetradentate f l u o r o s u l f ates are known. reported bidentate fluorosulfates are SbF^SO^F  71  The  only  and SeF^SO^F.  72  19 In both cases the structure i s assigned with the aid of  F nmr  other physical techniques and the v i b r a t i o n a l spectra are not understood, e.g. and  and well  for SbF^SO^F large discrepancies between the Raman  infrared spectra are observed.  Spectra of more bidenate fluoro-  sulfates w i l l be needed before any s t r u c t u r a l interpretations based on the positions of the S-0 fluorosulfate group was  stretching modes can be made.  A  tridentate 73  i d e n t i f i e d very recently for CoCSO^F)^  on the basis of infrared, Raman, u v - v i s i b l e , and magnetic measurements. The  SO^F  v S-F 3.  group was  found to have  symmetry with the p o s i t i o n of  raised from that of i o n i c fluorosulfates by about 100 cm  \  Other sulfonates Some work has also been reported on the v i b r a t i o n a l spectra of  other sulfonate anions. The frequencies of the SO^CF^  and  assigned with the aid of normal coordinate analyses i n two studies.  82 83 ' As shown i n Table 6, the two  considerably.  SO^CH^  the ions were  separate  — assignments for SO^CF^ disagree  The complications are caused by the extensive mixing  of v i b r a t i o n a l modes.  Vibrational spectra of some monodentate SO^CF^  - 22 TABLE 5 Stretching  F r eq u e n c i e s  V.so  Hainan  1400  1430  ir  1020  Table  6.  Previous  1081  1109  624  819  850  Band p o s i t i o n (cm-1)  Assignments  Tobias v  1230  v  1180  v  766  SO  6  8 2  Burger  s  CF_ 3  v  l (  a  S0_ 3  V  10  3  A)vsCF (  E  )  (A)'vvC-S  no  v5(A)6sS0  580  6 SO„ s 3  v8(E)6aCF  a  C F  3  no yes  SO3  6  yes  3  v.(A)v SO. 4 s 3  6  a  no  3  VF3  630  520  \)s?  Agreement  v7(E)vaS0  C F  3  8 3  CF_ 3  s  3  CF  a  V°3  S 0  s  Assignment  M.270  1038  for  ? 3  ^ so  1076 807  2  ^a  1237  865 690  P  1265  1224 1030  3  i r  Raman  1276 1290 1236  1216  2  Co(S05P)  3  ir  SO  Kode  SeF S03F'''2  SbP^SO^F71  a  3 i - & Tridentate  Oompoxmd  Mode  V so  for  v  l l (  1 2  E)6  a  no  3  S0  (E)PS0  no  3  3  no  353  PSO3  v  321  vC-S  (A)  no  208  PCF3  v9(E)pCF3  yes  3  yes  - 23 84 — 86 derivatives have appeared very recently  and as expected these  spectra show s p l i t t i n g of the E symmetry SO^ modes. assignment has also been made f o r the SO^Cl  A vibrational  anion.  In conclusion, v i b r a t i o n a l spectra should include Raman as well as i n f r a r e d spectra with the emphasis on the anion stretching modes and the C-Sn s k e l e t a l vibrations.  For l i q u i d s , polarized Raman  spectra should provide additional information and help assignment of the observed modes.  substantiate  The obtained information  should  reveal the f u n c t i o n a l i t y of the SO^F group but not whether the fluorosulfate acts as a bridging or chelating ligand. f i n a l d i s t i n c t i o n supporting such as X-ray d i f f r a c t i o n or  To make this  evidence from other physical techniques 119 Sn Mossbauer spectroscopy i s needed.  Physical properties, e.g. melting point, v o l a t i l i t y , or s o l u b i l i t y i n nonpftj ar solvents, may also provide additional clues. F.  Mossbauer Spectroscopy A second physical method which was used extensively i n the 119  investigation of the structures and the bonding i s 119 spectroscopy.  Since  Sn Mossbauer  Sn, one of the many n u c l e i which exhibits the  Mossbauer e f f e c t , has a reasonable natural abundance, 8.57%, i t s second Y~ Y energy i s i n a convenient range, and the h a l f - l i f e of 119 the f i r s t excited state i s optimal, Sn MOssbauer spectroscopy has been used extensively i n the study of the chemistry of t i n . An introduction ra  to the use of Mossbauer spectroscopy i n chemistry 88 by Greenwood.  has been written  - 24 -  1.  Principles The Mossbauer e f f e c t for t i n arises from r e c o i l l e s s emissions 119  and resonant reabsorption of y radiation by the  Sn atom.  119 Sn decays, as shown i n Figure 4, to i t s ground state by two Y  emissions and the second decay from the 3/2 nuclear excited state  to the 1/2 ground state i s the nuclear t r a n s i t i o n used to measure the Mossbauer e f f e c t for t i n . this decay are 23.875 KeV.  The energy of the Y rays emitted i n  This value i s not i n the range where  extremely low temperatures  are needed to e f f e c t r e c o i l l e s s emission  and absorption, however, 23.8 KeV i s a large energy and the source i s usually polymeric SnO^ imbedded i n a Y inert matrix to prevent recoil.  The absorber usually has to be cooled i n l i q u i d nitrogen to  prevent r e c o i l on the absorption of the  y-vays.  The h a l f - l i f e of —8  the f i r s t excited state (3/2 state) i s 1.84  x 10  range where Mossbauer l i n e widths w i l l be optimal. (< 10  sec and i s i n the Short h a l f - l i v e s  sec) r e s u l t i n lines with wide natural l i n e widths and —6  longer h a l f - l i v e s (> 10  sec) y i e l d l i n e s so narrow that serious  experimental d i f f i c u l t i e s are encountered i n their detection. The chemical applications of Mossbauer spectroscopy a r i s e from the fact that the spacings of the nuclear energy levels depend on the electron d i s t r i b u t i o n about the nucleus, i n p a r t i c u l a r on the d i s t r i b u t i o n of the valence electrons.  Thus i n a Mossbauer experiment,  the energy difference between the ground state and f i r s t excited state of  the source and absorber w i l l be d i f f e r e n t and resonant reabsorption  by the absorber of the Y Y r a  emitted by the source w i l l not be achieved.  In order to bring the source and absorber into resonance, the frequency  - 25 -  D e c a y of  Figure 4  Sn  H9  m  s t  Exc. State  3  /2  S n 119  •? 2 4 5  y 1  5 Q  =  State  V2  Kev f  +  I.84 x io  = 23.875  + Sn  Figure 5  d  65.66  / M Ground  m  Isomershift 8 ( mm  II9  /sec )  Mossbauer spectrum  Absorption  -1 r~ Velocity in Om m•! / s e c2  Excited state  3  A •>•  — r  Ground state Source  IS = Ea L  Absorber  Es„  77-Ze [lv// a d s ( O ) l - 1^/ s o u r c e ( O ) l ](<Rex - <Rg>) z  2  const. p €s  r  S Iv//  J  (Of  p o s if <Rex>!arger  < R g > a s for tin  _ s  sec  - 26 of the y emission i s modulated by moving the source r e l a t i v e to the absorber thus u t i l i z i n g the Ooppler e f f e c t .  The r e s u l t i n g Mossbauer  spectrum consists of a plot of the count of Y rays transmitted through the absorber against the v e l o c i t y of the source.  At some  v e l o c i t y there i s resonant absorption and the count rate drops.  2.  Isomer s h i f t The isomer s h i f t , 6 , i s the measure of the source v e l o c i t y needed  to bring a p a r t i c u l a r absorber into resonance with the source.  The  isomer s h i f t depends on the r a d i i of the nucleus and the s electron density at the nucleus according to:  6  where A r = r  =  Ar  2  • A|\JJS(0)|  const • —  . , ^ ^ - r , ^^ excited state ground state  A 1^8(0) | = |^s(0) absorber  | - |^s(0) | ' source  2  1  1  1  2  1  2  1  = difference i n s electron density at the nucleus, between the source and absorber. This equation shows that the isomer s h i f t i s dependent on a nuclear factor, Ar/r, and an extranuclear factor, A|I(IS(0)| .  For t i n , Ar/r  i s p o s i t i v e and therefore an increase i n <S indicates an increase i n I^ (0)absorber I ' ^ s  fc  e s  e  l  e  c  t  r  o  n  density at the absorber nucleus.  This means that 6 can be used as a measure of the s electron density at the t i n nucleus.  The v a r i a t i o n i n 6 from SnO^, customarily set at  0 mm/sec, for some tin(IV) compounds i s shown i n Figure 6.  - 27 -  Figure 6  Distribution of S for Sn(iv)  Sn n  increasing  bondpolarity  4+  dimethyltin(iv) derivatives  Sn 5s° 5 p °  S n (iv) 5s 5 p 1  3  1.1 — 1.6 mm/sec  -0.433 K SnF|  1.93 a-Sn(77°)  2  Snf^  —rO  r -0.5  0.80 SnCt  0.42 K SnCi  •  i  • SnBr. .  1.29 (CH,). Sn  4  Sri,  • 3 4  1  1.0  T  1.5  + 0.5  ( m m / s e c ) 2.0  SnO,  Quadrupole Coupling A  Figure 7  (mm/sec)  Absorption  V e l o c i t y in m m / s e c  +  -7-  5  Excited r _ 3 state  Ground j state  =  ±1-  L  Isomer shift  2  const  Quadrupole coupling  Q nuclear quadrupole q n~]  moment  electric Field gradient Asymmetry  Factor  for an axially s y m m e t r i c s y s t e m : A E = const. Q  V z z Q  - 28 3.  Quadrupole  splitting  Quadrupole s p l i t t i n g s , A, can arise i f there i s an e l e c t r i c f i e l d gradient, q, f o r any nuclear state which has a quadrupole moment, Q, i . e . f o r any state with spin greater than 1/2.  The f i r s t  119 excited state of  Sn has I = 3/2 so t i n compounds w i l l have a  quadrupole s p l i t t i n g whenever an imbalance of charge around the t i n nucleus causes an e.f.g. AEq  =  f o r t i n as given by the following equation.  1/2 e q Q ( l + n /3) '  =  A  V -V — ^ — . zz  where n i s an asymmetry factor equal to  The V's are the  components of the e.f.g. tensor.  For  a x i a l symmetry, n = 0 and A = const.q.,Q.-  I t can be seen from  these equations that both the magnitude and sign of A w i l l depend on the e.f.g., q.  For t i n compounds i t i s generally believed that  q arises primarily from i n e q u a l i t i e s i n the p o l a r i t i e s of the a bonds,  44  89 90 and not IT bonding effects as was once thought. '  The  size of q w i l l depend on two factors, charges on the atoms surrounding t i n , [q.. ], and the imbalance i n the d i s t r i b u t i o n of the la t valence electrons on t i n , t l ^ ] • These two contributions w i l l have c  v a  opposite signs  91  but t ^ ^ ]  > >  ^^.at^  92  anc  * '•Sral'' *  S  ^  e n c e  t  *  ie  dominant factor. The sign and magnitude of [ ^ ^ l H 1 W  also be dependent on two  factors, geometrical effects due to the d i f f e r e n t orientations of ligands about t i n and any imbalance i n the p o l a r i t y of the tin-ligand  - 29 -  a bonds.  The influence of geometry on A can be considered most 44 91 93  readily using the point charge approximation.  '  '  In this model  each ligand i s assumed to be a point charge and the contributions of the ligands [X] f o r the various geometries can be calculated [ x ]  q(x)(l-A(x)  =  r  V  and  zz  A a V  =  q  3  x  A  x  =  charge on X  =  shielding factor  Z(3cos 6-1)[X]  'Sn-X  x  (l/3r) +l) 2  zz  1 / 2  94 E l e c t r o n e g a t i v i t i e s or Taft inductive constants, estimate the a bond p o l a r i t i e s .  * a , can be used to  For compounds with the same geometry,  as the bond p o l a r i t y differences between the ligands increase, A w i l l also increase. The point charge model can also be used to predict quadrupole s p l i t t i n g s , i . e . i f the p a r t i a l quadrupole s p l i t t i n g f o r each ligand can be determined and the geometry i s known, then these can be used to predict  A.  Consistency between experimental A's and ones  calculated i n this manner can also be used as a check on the v a l i d i t y of the geometry assumed for the c a l c u l a t i o n . 4.  Room temperature e f f e c t At room temperature t i n compounds generally r e c o i l when emitting  or absorbing radiation and since the Mossbauer e f f e c t depends on r e c o i l l e s s emission and absorption no spectra are produced.  The fact  - 30 -  that " some t i n compounds do give spectra at room temperature has 95 96 been attributed to the polymeric nature of these compounds  '  because polymeric compounds w i l l have less freedom to r e c o i l thus exhibiting resonant absorption at higher temperatures than monomeric compounds w i l l . e  o n o  /e  0  The e f f e c t i s usually reported as the parameter R =  where the e's are the absorptions at the indicated temperatures.  R w i l l be i n the range of zero to one but experimental considerations cause the lower l i m i t to be % 0.03. The room temperature e f f e c t gives only a rough i n d i c a t i o n of possible polymeric nature. Exceptions to this r u l e , both polymeric compounds which do not have R > 0 and non-polymeric molecules with R > 0, are known.  This means the presence of a room temperature effect  can only be used as corroborative evidence and cannot be used as a basis for s t r u c t u r a l assignments. The s e n s i t i v i t y of the M8ssbauer parameters, p a r t i c u l a r l y the quadrupole s p l i t t i n g s , to changes i n the environment around t i n can be i l l u s t r a t e d by reference to the data for trimethyltin carboxylates, Table 7, which indicate the s e n s i t i v i t y of this technique to changes i n the X group i n CO^CX^. G.  HSO^F as a Non-aqueous Solvent System The use of f l u o r o s u l f u r i c acid as a solvent system has been  extensively i n v e s t i g a t e d ^ 1  1(  ^ and the whole subject of f l u o r o s u l f u r i c 2  49 acid chemistry has been reviewed. are l i s t e d i n Table 8.  Some physical properties of HSO^F  The large l i q u i d range of HSO^F allows  measurements and reactions to be performed over a wide temperature range.  Although the freezing point i s low cryoscopic measurements can  -5 31 T  TABLE 7 Trimethyltin mm/sec  Compound (0H ) 3 S n C 0 C H 3  2  1.35  3  2  3  C0 CBr3 2  C0 N (CHx) 2  P  •A nun/s e c  reference  3.68  97 98 98 93 98 93 93 99 99  3.89 4.08 3.90 4.15 4.22 4.13 3-56 3.39  1.37 1.34 1.44 1.33 1.43 1.32 1.26  2  OO2OOI3 2  •  1.41  OO2OH2OI C0 CHC1 OOoGHoBr  00 CF  carboxylates  TABLE 8 P h y s i c a l Properties of Property B o i l i n g pt (*0) Freezing p t A * C ) Density ( d . ° ) Viscosity (centipoise) D i e l e c t r i c constant S p e c i f i c conductance (ohin" Self ionization 2HSO3F  ^ = ^ 1  HSO3F  Value  (temp)  162.7 -88.98  1  cm" ) 1  equation H2S03F"*" +  SO3F"  1.726 (25) I.56 (25) 120(25) 1.06 x 10"^ (25)  Reference 100 102  100 100 100 100  - 32 -  s t i l l be made.  102  The low s p e c i f i c conductance, K, of HSO^F allows  conductometry because the proton jump mechanism i s operative.  The  r e l a t i v e l y low v i s c o s i t y means contributions from other ions w i l l be more noticeable i n HS0„F than i n H„SO.. 3 2 4 49 F l u o r o s u l f u r i c acid i s perhaps the strongest simple acid known and only a very limited number of solutes are expected to behave as acids i n this system, i . e . give r i s e to ^SO^F"*" ions.  Sulfur t r i o x i d e  as well as the inorganic f l u o r i d e s AuF^, PtF^, TaF,. and SbF,. are acids but only SbF,.  and SbF^-SO^ mixtures"*"^ have been studied extensively.  Some examples of bases are metal fluorosulfates such as KSO^F, s a l t s of inorganic acids such as KF or KCIO^, inorganic acids f o r example I^SO^, as well as other inorganic or organic molecules which can be protonated. Measurements of the s p e c i f i c conductance of a f l u o r o s u l f a t e containing solute i n HSO^F at d i f f e r e n t solute concentrations w i l l give information on the extent of the d i s s o c i a t i o n of the solute into ions. Because of the high m o l a l i t i e s of the H^SO^F" " and SO^F 1  ions, the s p e c i f i c  conductance of the solution w i l l depend on Y, the number of moles of SO^F  or ^SO^F" * ions produced i n solution per mole of solute. Y can 1  be calculated by comparing the molality of a solution which has some s p e c i f i c value of K with the molality of the solution of the f u l l y dissociated base KSO^F which has the same s p e c i f i c conductance. Y w i l l be the r a t i o of m KSO^F  /m  - ^. . solution  Some advantages of f l u o r o s u l f u r i c acid as a solvent system are: (1)  the common anion should f a c i l i t a t e the i n t e r p r e t a t i o n of  conductivity r e s u l t s , (2)  the acid can be used as both a non-aqueous solvent and a  - 33 -  reactant, (3)  and HSOgF can be e a s i l y p u r i f i e d .  There has been one  study of tin(IV) compounds i n 100%  sulfuric  103 acid.  Tetramethyltin and  trimethyltin sulfate were found to  dissolve rapidly to form solvated and  trimethyltin cations.  t r i p h e n y l t i n hydroxide dissolve i n ^SO^  of Sn-C  bonds to form the HSn(HS0 ) 4  6  and  If the expected range of inorganic  Tetraphenyltin  with complete cleavage 2-  SnCHSO^Jg  ions.  and organometallic t i n fluoro-  sulfates can be prepared as well as analogous derivatives of other sulfonic acids, their study should help to clear up controversies mentioned above; such as the existence or non-existence of organotin cations  i n solution and i n the s o l i d state.  This wide range of  compounds should also be h e l p f u l i n establishing the chemical s i g n i f i cance of Mbssbauer parameters as well as i n investigating  the  a p p l i c a b i l i t y of v i b r a t i o n a l spectroscopy to s t r u c t u r a l studies of this type.  - 34 -  CHAPTER I I EXPERIMENTAL  A.  Apparatus Because many of the compounds handled during this investigation  were hygroscopic, techniques which avoided the contact of these compounds with a i r were necessary.  For this reason s o l i d s and non-  v o l a t i l e l i q u i d s were handled i n a dry box and v o l a t i l e l i q u i d s and gases, on a vacuum l i n e .  1.  Dry box The dry box was a Vacuum Atmospheres Corporation Model HE-43-2  Dri-Lab with a Model HE-93-B Dri-Train. for the atmosphere i n the dry box.  "L" grade nitrogen was used  The dryness of the nitrogen was  maintained by c i r c u l a t i n g i t through a regeneration chamber f i l l e d with Lindes Molecular Sieves.  The sieves were regenerated p e r i o d i c a l l y  by heating them i n the presence of a i r .  2.  Vacuum l i n e s The general purpose glass vacuum l i n e consisted of a 50 cm long  piece of 2 cm glass tubing with four outlets connnected  to a mechanical  rotary vacuum pump v i a a Fischer and Porter teflon stem stopcock, a standard taper B19 ground glass cone-socket connection f o r removing  - 35 -  the l i n e , and two safety traps.  The four outlets consisted of teflon  stem stopcocks and BIO ground glass sockets, three spaced equally along the lower side of the l i n e and the fourth at the end of the line.  A mercury manometer which could be isolated from the rest of  the l i n e v i a a stopcock was  also incorporated into the system.  A metal vacuum l i n e made of 1/4" equipped with Whitey valves to the glass l i n e , was  diameter monel tubing  and  (1KS4316) which worked i n a manner similar  also available for handling substances reactive  towards glass.  3.  Reaction  vessels  Several types of glass reaction vessels and one type of metal reactor were used during this work. (a)  Glass  The simplest type was  a two part glass reactor which consisted  of a 50 ml round bottomed flask with a standard  taper B19 ground glass  cone and an adapter top consisting of a t e f l o n stem stopcock between a B19  socket for attachment to the f l a s k and a BIO cone for attachment  to the vacuum l i n e .  This type of reactor had the advantages that i t  could be readily opened to put i n solids or l i q u i d reactants and also to take out products,  and i t could also be attached  to the vacuum  l i n e for the addition or removal of v o l a t i l e l i q u i d s .  The main  disadvantages of this reactor were that because of i t s two part construction i t could not be used with gases which were at a pressure of greater than one atmosphere and because i t had a ground glass j o i n t which had to be greased, i t could not be used whenever grease attack  - 36 would be a problem. These two disadvantages could be overcome by using a one part reactor which could be sealed closed a f t e r s o l i d reactants had been added.  Reactors of this type with several d i f f e r e n t shapes were used.  The simplest one consisted of a test tube with a c o n s t r i c t i o n and B19  cone  at the top and a side arm leading to a BIO cone v i a a t e f l o n  stem stopcock.  After s o l i d s were added (in the dry box, i f necessary)  through the c o n s t r i c t i o n and the B19 cone capped, the vessel could be flame-sealed  at the c o n s t r i c t i o n and v o l a t i l e reactants d i s t i l l e d into  the r e s u l t i n g one piece grease free reactor on a vacuum l i n e .  Two  other reactors which worked on the same p r i n c i p l e s were also used. These were the same as the one part reactor described above except that greater volumes were attained by using 50 ml round bottomed flasks or 125 ml  erlenmeyer flasks instead of simple tubes.  For reactions between two v o l a t i l e reactants, a simpler vessel without the c o n s t r i c t i o n and B19 cone could be used.  These reactors  consisted of test tubes or bulbs with t e f l o n stem stopcocks and BIO cones attached d i r e c t l y to the top of the tube or bulb. were also used to store v o l a t i l e l i q u i d s .  Similar vessels  The one part reactors could  only be used once and had to be broken open inside the dry box to remove s o l i d products.  However, they allowed a complete exclusion of stopcock  grease and would hold a p o s i t i v e pressure of several atmospheres. Teflon coated s t i r r i n g bars could be used to s t i r reaction mixtures externally.  - 37  T  r = 0  hoke  V a l v e ( N o 431)  • Monel Metal  Tube  S o f t s to S e c u r e L i d to B o t t o m V e s s e l  Figure 8  Lid  Reactors  C o n d e n s e r Inlet Bottom  "V.  • C o n d e n s e r Inlet  fvtonel  Metal R e a c t i o n Vessel ( 1 5 0 ml )  Monel Metal a - P e r t Reaction Vessel  B 19 C o n e 1 — S I O Ccrs. Fischer c n i Porter Teflon Vclve  135 m l PyrexErler.m'eyer Flask  Two P a r t G l a s s E e a c t o r  One P a r t G l a s s E e a c t o r s  - 38 -  () b  Metal  A suitable metal reactor used i n this study consisted of a c y l i n d r i c a l monel pot of % 100 ml volume connected with six bolts to a l i d equipped with a Hoke valve (#431).  A vacuum tight seal was  achieved  with a teflon ring inserted into 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 vacuum l i n e using a swagelok connector.  4.  F l u o r o s u l f u r i c acid The apparatus and techniques involved i n the p u r i f i c a t i o n have  been d e s c r i b e d . T e c h n i c a l grade HSO^F was doubly d i s t i l l e d  and  for conductivity work d i s t i l l e d d i r e c t l y into the conductivity c e l l . Before d i s t i l l a t i o n L grade  was passed through the c e l l and  for several hours and the entire apparatus was to remove moisture or traces of HF. of between 1.1 x 10  -4  and 1.3 x 10  flamed out p e r i o d i c a l l y  HSO^F with a s p e c i f i c conductivity  -4  ohm  -1  cm  -1  was obtained i n this -4  manner.  5.  still  The lowest reported value i s 1.08 x 10  -1 ohm  -1 cm  Conductometry The design of the conductivity c e l l has been d e s c r i b e d . I t i s  a three electrode c e l l with c e l l constants of ^ 3, 7 and 10 cm ^ 104 with platinum electrodes p l a t i n i z e d p e r i o d i c a l l y with platinum black. The c e l l was calibrated using aqueous K C l . ^ ^  Conductivity measurements  were made using a Wayne Kerr Universal Bridge, B221A, while the c e l l was kept at a constant temperature  of 25.00 + 0.01°  (Brookly precision  thermometer) i n an o i l bath with a volume of ^ 9 1. with a Sargent Model ST  Thermonitor.  - 39 -  Determination of the s p e c i f i c conductivity of a s o l i d solute over a range of concentrations was done by making several additions of known amounts of the solute from a dropping funnel designed for the addition of s o l i d samples i n the absence of moisture to a known weight of HSO^F i n the conductivity c e l l and recording the conductance after each addition.  This funnel was simply a large bore glass  stopcock with an enclosed cavity f o r the sample above the tap and a narrow tube and BIO cone below.  6.  V i b r a t i o n a l spectroscopy Infrared spectra over the range of 4000-250 cm ^ were recorded on  a Perkin Elmer 457 grating spectrophotometer.  Solid samples were run  as nujol mulls, or i n the cases where the samples attacked nujol, as thin films, using AgCl, AgBr, KRS5 (TIBr-TlI), or C s l windows obtained from Harshaw Chemicals.  The KRS5 and Csl windows are transparent over  the whole spectral range of the spectrometer, however, these windows are not very inert and could not be used for many samples due to window attack.  In these cases AgBr, transparent to ^300  transparent to ^400  cm \  were used.  cm \  or AgCl,  Spectra of gases were obtained  using a monel metal gas c e l l of 7 cm path length with AgCl windows. This c e l l could be attached to a vacuum l i n e v i a a Whitey valve and B10 cone.  Infrared spectra were calibrated using a polystyrene f i l m .  Raman spectra were recorded on a Cary 81 spectrophotometer  with a  o  Spectra Physics Model 125 He-Ne laser l i g h t source (X = 6328 A). of s o l i d samples were recorded with the sample sealed into 6 mm glass tubes with a f l a t  end.  Spectra OD  - 40 -  7.  MBssbauer spectroscopy The Mossbauer spectrometer was of the constant acceleration type  and consisted of a TMC Model 305 v e l o c i t y tranducer driven at constant acceleration by a TMC Model 306 wave form generator which also synchronized the 400 channel analyzer.  The source, BaSnO^ enriched with  ^"^ Sn, was mounted on the transducer. m  y Rays transmitted through the  absorber were detected by a Reuter-Stokes  -  RSG 60 proportional counter  and fed into a Nuclear Chicago Model 33-15 single channel analyzer and then to a 400 channel memory.  The output was displayed on a  Hewlett Packard Model 120B oscilloscope and also printed out on an IBM Model 44-16 typewriter.  The output of the spectrometer was  f i t t e d to a Lorentzian curve on an IBM 360/67 computer and information about peak i n t e n s i t y , isomer s h i f t and quadrupole s p l i t t i n g were obtained i n terms of channels.  The v e l o c i t y was calibrated with a  National Bureau of Standards sodium nitroprusside c r y s t a l absorber with 119 a A of 1.726 mm/sec.  Isomer s h i f t s were calibrated with an  enriched SnO^ absorber.  Sn  Samples were placed i n brass c e l l s with mylar  windows and spectra were recorded with the absorber either at 78° or 298°K.  Cells f i t t e d with t e f l o n windows were used for samples which  reacted with the mylar.  Isomer s h i f t s are reported r e l a t i v e to Sn0  2  with an estimated p r e c i s i o n of + 0.03 mm/sec. 8.  Nuclear magnetic resonance spectroscopy 19  1 F and H nmr spectra were both obtained on a Varian HR 60 19  spectrometer.  For  F nmr CFCl^ was used as an external standard and  for "4l nmr (CH^^Si was used, also external.  Samples were placed i n 5 mm  diameter tubes and either flame sealed or capped.  - 41 9.  Melting points Melting points were determined using a Thomas Hoover c a p i l l a r y  melting point apparatus i n which both the sample under study i n a glass c a p i l l a r y and the thermometer bulb are heated i n an o i l bath.  The  melting points are reported uncorrected.  10.  Analyses Elemental analyses f o r Sn, F, S, As, Sb, and CI were obtained  from A. Bernhardt Microanalytical Laboratories i n Germany.  Carbon and  hydrogen analyses were carried out by Mr. P. Borda of the Chemistry Department, University of B r i t i s h Columbia.  For some compounds, t i n  and chloride were determined i n our laboratory.  T i n was estimated  gravimetrically as SnO^ and chloride by potentiometric t i t r a t i o n using a Radiometer Model 26 pH meter.  B.  Chemicals  1.  Commercial sources Most of the chemicals used i n the preparations were obtained from  commercial sources and were of reagent grade or the highest grade available.  The chemicals, sources and any remarks are l i s t e d i n  Table 9.  2.  Literature preparations Some of the s t a r t i n g materials which were not commercially  available were prepared by methods described i n the l i t e r a t u r e as outlined below.  - 42 -  TABLE  9  Chemicals Chemical '(CH3)4Sn (CH^USnCl (OH^)pSnClp (CHv)BnCl, SnCl 4 SnBr SnF^  S1C1 TiCl  4 4  GeCl4 SbF5  AsFpBF J  3  CsCl NO  N0 ci  ?  2  BrS SO,  BaCS03CF ) 3  HS03F  HSO3CI H3O3CE3 HS0vC H5 NOSO4H so ci 2  2  2  Source  Remarks  P e n n i n s u l a r Chem R e s Alpha. Ventron Ozark Mahoning, P.C.R. Alpha Ventron B.& A . , B.D.H. Alpha Ventron R e s e a r c h Inorg Chea Alpha Ventron B.D.H.  Organic  Eastman,  B.D.Hv.  vacuum  CHCI3  from  distilled  distilled  Ozark Mahoning Ozark Mahoning .Matheson B.D.H. Matheson Matheson Matheson B.D.H. Allied Allied 3M Allied i'latheson Eastman Eastman Columbia  recrystalized  i n N2  stream  to  remove  Tech, doubly distilled not p u r i f i e d , see r e f 106  Chem  obtained as a l i q u i d , due t o e x c e s s H S 0 2  4  probably  HP  - 43 -  Peroxydisulfuryl d i f l u o r i d e , S„O^F , was prepared by the AgF Z b Z Z 0  catalyzed reaction of fluorine with sulfur trioxide at 180-220° using the method described by Cady and S h r e e v e . T h e c a t a l y t i c reactor and method were e s s e n t i a l l y the same as reported, however, the following changes were made to increase the y i e l d .  A larger reactor  120 cm long (vs. 90 cm) and a reaction temperature of 180° was to give better r e s u l t s .  found  The S 0 ^ was also heated to 50° (vs. 25°).  To avoid the condensation of p o t e n t i a l l y hazardous FSO^F the l a s t trap was cooled to only -78°C (dry ice) and not -183° ( l i q u i d 0^) as done i n the l i t e r a t u r e preparation. Unreacted SO^, i f present, was removed from the crude $2^6^2 ^ funnel i n a fumehood.  washing with 96% HL^SO^ i n a separatory  Impurities of FSO^F were removed by pumping  on the S„0,.F- at -78° f o r extended periods of time. The purity of Z o Z 19 the f i n a l product was checked by infrared and F nmr. Bromine monofluorosulfate was prepared by the d i r e c t reaction of excess Br_ with S 0,,F- as reported by Cady. Z  108  o  Z b Z  Bromine t r i s f l u o r o -  sulfate was prepared by the reaction of bromine with excess S„0,F_ Z  O  Z  108 at room temperature. Iodine t r i s f l u o r o s u l f a t e was prepared by the similar reaction of iodine with excess S_0,F also at room temperature. Z b Z  Chlorine dioxide was prepared from potassium chlorate, oxalic 109 acid and s u l f u r i c acid using the method described by .Brauer.  The  CIO2 produced was p u r i f i e d by pumping on i t at -78° to eliminate CO2 and by trap-to-trap d i s t i l l a t i o n .  Because of i t s explosive nature,  the CK>2 was not allowed to warm up but was reacted immediately with S.0,F„ to produce C10_S0„F.^® A l l operations involving C10_ were Z  O  Z  Z  5  carried out i n a fumehood with blackened windows.  Z  - 44 -  N i t r o s y l chloride was prepared fron n i t r o s y l hydrogen sulfate, NOSO^H, and sodium chloride following the procedure described i n Brauer's Handbook.^"'""'' Potassium hexachlorostannate and cesium hexachlorostannate were prepared from aqueous SnCl^ and an excess of the 112 a l k a l i metal halide following the procedure f o r K^SnCl^.  Nitrosyl 113  hexachlorostannate was prepared from N0C1 and anhydrous SnCl^. Trifluoromethanesulfonic acid was prepared from BaCSO^CF^)^ and fuming s u l f u r i c acid by J.R. D a l z i e l i n our laboratory.  More recently  HSO^CF^ has become available from the 3M Company. C.  Suppliers of Materials and Equipment The suppliers f o r some of the materials and equipment used i n  this work are l i s t e d here. Swagelock f i t t i n g s , Columbia Valve and F i t t i n g Co., Vancouver, B.C. Metal f i t t i n g s using metal or teflon seals to j o i n pieces of metal tubing. Whitey valves, 1KS4, Columbia Valve and F i t t i n g Co. and Hoke valves, #431, Hoke Inc., C r e s k i l l , N.J., high vacuum metal values. Whitey valves had the advantage that they could be disassembled f o r cleaning or refurbishing. Fischer and Porter 4 mm teflon stem stopcocks, Fischer and Porter, Warminster, Pa., Kontes valves, Kontes of I l l i n o i s , Franklin Park, I l l i n o i s , and Rotaflow valves, Quickfit and Quartz, Staffordshire, England. Greaseless taps for glass systems which produced vacuum tightness v i a a t e f l o n to glass seal.  - 45 -  Teflon coated s t i r r i n g bars, Canlab, Vancouver. Molecular sieves, Linde A i r Products, distributed by Fisher Scientific. Infrared c e l l windows, Harshaw Chemical Corp., Cleveland, Ohio. AgCl, AgBr, KRS5, and C s l windows 0.5 cm x 2.5 cm diameter and AgCl and AgBr sheets 1 mm thick.  - 46 -  CHAPTER I I I METHYLTIN SULFONATES  A.  Introduction  1.  Previous work Organotin derivatives of a wide range of oxyacids including  sulfates,  114,115  are known.  . 116-118 118 . . . . 119-121 nitrates, perchlorates, and carboxylates t  These compounds were usually prepared by the s i l v e r s a l t  method, e.g.  118 (CH ) SnCl 3  3  +  AgC10  *-  4  (CH ) SnC10 3  4  +  AgCl  Most of these compounds are dimethyltin or t r i m e t h y l t i n derivatives, 31 however, some monomethyltin compounds such as methyltin t r i n i t r a t e 119 121 121 and mixed methylhalotin derivatives ' such as (CH^)^ClSnCOOCH^ are reported. The number and variety of s u l f o n i c acid derivatives i s more limited.  Before our study began (CH )2Sn(S0 CH )2 had been prepared 3  3  3  79  and (CH ) S n S 0 C H by i n s e r t i o n of SQ 78 into a tin-carbon bond i n (CH^^Sn. Some other d i a l k y l t i n  by the s i l v e r s a l t method  3  3  3  3  bismethane- and bisethanesulfonates were prepared by reaction of 79 d i a l k y l t i n oxides with the appropriate s u l f o n i c acids,  and the  reaction of (C^Hg^SnO with paratoluenesulfonic acid was used to  3  - 47 -  prepare d i b u t y l t i n bistoluenesulfonate. preparations of (CH^SnSC^F and  122  Since our work began, the  (CH ) SnSC> CF by the reactions of 3  3  3  3  76 ((CH ) Sn) 0 with 3  3  and ^ ^ ( ^ ^  2  r e s  P  e c t i v e l  y  w  e  r  reported  e  as well as the much simpler preparations of (CH ) SnSC> CF , 3  (CH ) Sn(S0 CF ) 3  2  3  3  2  and  (CH ) Sn(S0 C F ) 3  2  3  2  5  2  3  3  3  by the s o l v o l y s i s of (CH ) Sn  i n the appropriate amounts of the s u l f o n i c a c i d s .  3  4  7 7  The following comments can be made about the previous work on methyltin sulfonates. (1)  Only dimethyltin bisulfonates or t r i m e t h y l t i n sulfonates are  reported, there are no reports of monomethyltin sulfonates or mixed derivatives such as methylhalotin sulfonates. (2)  The preparative routes are usually tedious and often require  s t a r t i n g materials which are d i f f i c u l t to obtain or handle.  2.  (3)  A general u n i f i e d preparative method i s lacking.  (4)  No s t r u c t u r a l studies have been attempted.  Promising Two  routes to sulfonates  promising preparative routes which should complement each  other are s o l v o l y s i s reactions i n the s u l f o n i c acids and ligand r e d i s t r i b u t i o n reactions. (a)  Solvolysis  Acid s o l v o l y s i s has found previous application i n organotin  chemistry  . ,. 119,123,124 , , . ... 125,126 using carboxylic acids or hydrogen halides as solvents and t e t r a a l k y l t i n s or t e t r a v i n y l t i n s as substrates.  These  reactions generally r e s u l t i n cleavage of one or two tin-carbon bonds, 127 but i n exceptional cases a l l four Sn-C  bonds are broken.  The  - 48 -  mechanism for the substitution was  shown i n the case of the hydrogen 126  halides to be two competitive consecutive second order reactions  l — R „ S n C l 3 k  R,Sn 4  +  HC1  2 — R  +  RH  2  +  k  R SnCl 3  +  HC1  2  S n C l  RH  At the outset of this study mainly cleavage of tin-carbon bonds had been reported and no systematic study involving methyltin halides, for example, had been made.  More recently, the s o l v o l y s i s of triorgano-  t i n chlorides i n perfluorocarboxylic acids r e s u l t i n g i n the p r e f e r e n t i a l cleavage of the tin-carbon bond to form d i a l k y l c h l o r o t i n perfluorocarboxylates has been reported."'"  (b)  Ligand  28  redistribution  Ligand r e d i s t r i b u t i o n reactions are an area of preparative chemistry which has been extensively studied for many organometallic systems including organotin compounds.  Much of this work has been  reviewed f a i r l y recently and the general topic of ligand r e d i s t r i b u t i o n 13 has been discussed extensively.  129 '  A common type of ligand r e d i s t r i b u t i o n reaction i s one, exemplified by mixtures of t i n halides, i n which a s t a t i s t i c a l d i s t r i b u t i o n of a l l possible combinations i s produced, e.g. SnCl. + SnBr. 4 4  — ——  SnCl.Br + SnCl.Br. + SnClBr. 3 L I 3  130  - 49 A second type, more appealing from a preparative point of view, i s a ligand r e d i s t r i b u t i o n reaction i n which only one product i s formed preferentially.  Examples of reactions of this type are the preparations  of a l k y l t i n and a r y l t i n halides from t i n tetrahalides and 131  132  or t e t r a v i n y l t i n s ,  3R,Sn 4  '  +  tetraalkyltins  e.g.  4R SnCl  SnCl. 4  132  3  In these reactions single products could be obtained by using the appropriate concentrations of the reagents.  Only one example of a  ligand r e d i s t r i b u t i o n reaction of an oxyacid i s known, the r e d i s t r i b u t i o n 121 reaction of an organotin carboxylate with a diorganotin dichloride.  R SnCl  2  +  R SnCl  2  + 2R^SnC00R"  2  and  2  B.  Preparations  1.  (CH ) Sn(S0 X) 3  2  R SnClCOOR" + R^SnCl  R^SnCOOR"  3  2  R Sn(COOR") + 2R^SnCl 2  2  2  Dimethyltin b i s f l u o r o s u l f a t e was prepared by the s o l v o l y s i s of either ( C H ^ S n , ( C H ^ S n C l or ( C H ^ S n C ^ i n an excess of HS0 F at 3  room temperature.  Methane was a byproduct when (CH^^Sn was used,  methane and HC1 when ( C H ^ S n C l was used and HC1 with HSO (CH ) Sn 3  4  (CH ) SnCl 3  3  +  2HS0 F  F - (CH^Sn^F^  3  +  (CH^SnCl^  2HS0 F 3  HSO F ^  +  (CH ) Sn(S0 F) 3  2  3  2  2CH  +  CH  4  4  +  HC1  - 50 -  (CH ) SnCl 3  2  +  2  2HS0 F 3  HSO F ^  (CH ) Sn(S0 F) 3  2  3  +  2  2HC1  A t y p i c a l reaction with (CH > SnCl was carried out by d i s t i l l i n g an 3  3  approximately f i v e - f o l d excess of HS0 F onto one to two grams of dried 3  (CH > SnCl i n a two part round bottom f l a s k reactor. 3  3  The  (CH^SnCl  reacted immediately with the evolution of HC1 to produce a clear solution.  Approximately ten minutes l a t e r methane was evolved, and  clear p l a t e - l i k e crystals precipitated out. These crystals were then f i l t e r e d and washed with HS0 F. 3  I f a larger excess of HS0 F was used 3  i n the reaction the product remained i n solution and could be isolated by removing the HS0 F by vacuum d i s t i l l a t i o n .  In this case the y i e l d  3  i s v i r t u a l l y 100%, e.g. i n one preparation 1.83 g (9.20 mmoles) of (CH ) SnCl yielded 3.22 g (9.29 mmoles) of ( C H ) S n ( S 0 F ) . 3  3  3  (CH ) Sn(S0 F) 3  2  3  2  3  2  The  forms as hygroscopic colorless p l a t e - l i k e crystals  2  which melt with decomposition at 253°.  The stoichiometry was  established by elemental analysis of C, H, Sn, S, and F. This reaction could not be arrested after the f i r s t step.  This  was t r i e d both by using a greater excess of HS0 F i n an attempt to form 3  a stable solvated ( C H ) S n 3  cation which might not react further and  +  3  by running the reaction at lower temperatures. (CH ) Sn(S0 CF ) , 3  2  3  (CH ) Sn(S0 C H^) 3  2  3  2  3  2  2  ( C H ) S n ( S 0 C l ) , ( C H ^ S n ^ C H ^ and 3  2  3  2  can be prepared by analogous reactions using the  appropriate sulfonic acids but higher reaction temperatures and longer reaction times have to be used f o r the less reactive methane- and ethanesulfonic acids.  Previous reports  gave melting points of 327° (CH ) Sn(S0 Me) . 3  2  3  2  7 7  on dimethyltin bissulfonates  for (CH ) Sn(S0 CF ) 3  2  3  3  2  and 325°  7 9  for  - 51 -  Table 10.  Dimethyltin Sulfonates.  Compound  Analysis  mp  Calculated (CH ) Sn(S0 F) 3  2  3  253  2  (CH ) Sn(S0 CF ) 3  2  3  3  (CH ) Sn(S0 Cl) 3  2  3  336-7  2  370-5  2  (CH ) Sn(SO CH )3  2  (CH ) Sn(S0 C H ) 3  312  2  2  3  2  5  272  2  (CH ) Sn(S0 C H CH ) •2H 0 3  2  3  6  4  3  (CH ) Sn(S0 C H CH ) 3  2  3  6  4  3  2  2  2  >300  (%) Found  C  6.92  7.01  H  1.72  1.80  Sn  34.22  34.54  S  18.49  18.67  F  10.96  11.09  C  10.74  10.70  H  1.35  1.50  F  25.51  26.52  C  6.06  5.04  H  1.59  3.04  CI  18.67  15.4  C  18.54  18.37  H  4.67  4.59  C  19.62  19.78  H  4.39  4.11  C  36.45  36.18  H  4.58  4.13  C  39.10  39.25  H  4.11  4.0  - 52 (CH ) Sn(£-S0 C H CH ) «2H^O can be prepared by reacting 3  (CH ) SnCl 3  2  2  2  3  6  4  3  2  and paratoluenesulfonic acid i n aqueous solution at room  temperature and c o l l e c t i n g the r e s u l t i n g insoluble s o l i d product on a f r i t . The anhydrous s a l t can be obtained by heating the hydrate to 120°.  A reaction similar to the one used to prepare (CH„)_Sn(S0„C-H.CH„) • J 2 3 o 4 3 z  2H 0 using ( C H ) S n C l 2  3  2  (CH ) Sn(SC* CH ) . 3  2  3  3  2  and HS0 CH produced [ ( C H ) S n C l ] ^ and not 3  3  3  2  The product was i d e n t i f i e d by comparing i t s  2  infrared spectrum and melting point to those of [ ( C H ) S n C l ] 0 . 3  2.  2  2  (CH ) Sn Derivatives of oxyacids 3  2  The dimethyltin derivatives of some other oxyacids were synthesized either by l i t e r a t u r e methods"'" > 133,134 ^ 22  solutions of ( C H ) S n C l 3  2  m  i i g x  saturated aqueous  n  with aqueous solutions of the acids or the  2  sodium s a l t s of the acids. of  ^  The (CH ) Sn s a l t s a l l precipitated out 3  2  solution as very fine precipitates and could be f i l t e r e d and then  dried i n an oven at 120°.  Several s a l t s precipitated out as the basic  s a l t s , i . e . as (CH ) SnA 'OSn(CH ) . 3  2  2  3  2  A n a l y t i c a l results are l i s t e d  in Table 11.  3.  CH ClSn(S0 X) 3  3  2  Methylchlorotin b i s f l u o r o s u l f a t e could also be prepared by a s o l v o l y s i s reaction i n HS0 F. 3  onto 0.500 g (2.08 mmoles)  When an excess of HS0 F was 3  of CH SnCl 3  3  distilled  i n a round bottomed f l a s k ,  HC1 was evolved and a clear solution formed.  If the HS0 F was removed 3  by vacuum d i s t i l l a t i o n , 0.765 g (2.08 mmoles) of CH ClSn(S0 F) 3  3  2  was  i s o l a t e d as a hygroscopic white c r y s t a l l i n e s o l i d which decomposed at 162°.  - 53 Table 11.  Elemental Analyses of (CH ) Sn Salts.  Compound  C (%)  H  C/o)  Calculated  Found  Calculated  36.30  36.24  3.92  3.83  39.02  39.24  4.21  4.29  11.61  11.11  3.01  2.80  8.61  8.59  3.62  3.54  9.95  9.32  2.52  2.62  27.53  27.66  3.18  3.03  29.77  29.90  3.61  3.52  17.05  17.20  4.29  4. 00  134 (CH ) SnC H 0 -(CH ) SnO *  22.19  22.36  3.76  3.47  (CH ) SnC H 0  38.38  37.10  3.22  2.91  10.83  10.68  2.72  2. 80  7.77  8.15  1.96  2.05  (CH ) Sn(C H P0 H) 3  2  6  5  3  2  (CH ) Sn(C H P0 H) 3  2  6  5  2  [(CH ) Sn] (P0 ) 3  2  3  4  1 2 2 2  2  122 (CH ) Sn(H P0 ) 3  2  2  2  2  133 [(CH ) Sn] (As0 ) 3  2  3  2  J  4  (CH ) SnC H As0 3  6  5  2  133 3  (CH ) SnC H CH As0 3  2  6  5  2  3  133 (CH ) Sn[(CH ) As0 ] LJJ  3  2  3  2  2  2  3  3  2  3  2  4  4  8  4  4  3  2  4  (CH ) SnW0 -(CH ) SnO 3  2  4  (CH ) SnMo0 3  2  3  134 4  Found  2  - 54 HSO F CH SnCl 3  +  3  2HS0 F  CH ClSn(S0 F)  3  3  3  +  2  The stoichiometry was established by elemental analysis. CH SnCl 3  3  2HC1  Solutions of  i n HS0 F i n one part erlenmeyer reactors were heated eventually 3  to 140° i n attempts to prepare CH Sn(S0 F) 3  3  These attempts were a l l  3>  f a i l u r e s , and the products were i d e n t i f i e d as Cl^SnCSO^)^ presumably via: HSO F CH SnCl 3  + 2HS0 F  3  CH ClSn(S0 F) 3  3  CH ClSn(S0 CF ) 3  3  i n HS0 CF . 3  3  CH ClSn(S0 F)  3  3  2  2  +  3  HC1  3  HSO F — C l S n ( S 0 2  +  2  F )  3  2HC1  2  +  CH  4  was prepared by a similar s o l v o l y s i s of CH SnCl 3  When a solution of CH SnCl 3  3  3  i n HS0 CF was heated a t i n ( I I ) 3  compound tentatively i d e n t i f i e d as S n ( S 0 C F ) 3  3  2  3  was produced. No attempts  were made to extend this work by preparing derivatives of HS0 C1, 3  HS0 CH or HS0 C H . 3  4.  3  3  2  5  (CH ) SnS0 X 3  3  3  Trimethyltin fluorosulfate was prepared by slowly adding HS0 F from 3  a burette to an approximately three-fold excess of (CH^.^Sn-.cooled to -90' i n a 50 ml round bottomed-  flask.  The burette was attached to the  f l a s k by a B19 ground glass union i n order to keep the reactants and products isolated from the atmosphere.  After addition of the HS0 F 3  the burette was replaced by a teflon stem stopcock adaptor through which the flask could be attached to the vacuum l i n e .  These components  - 55 Table 12.  Other Methyltin Sulfonates,  Compound  CH ClSn(S0 F) 3  3  3  3  3  (CH ) SnS0 F 3  3  3  3  (CH ) ClSnS0 F 3  2  3  CH Cl SnS0 F 3  2  3  2  178-80  109-11  3  (CH ) SnS0 CH 3  161-2  2  CH ClSn(S0 CF )  3  Analyses  mp  144-5  108  112-5  Calculated  Found  CI  9.68  9.84  S  17.46  17.70  F  10.35  10.33  S  14.04  13.85  F  24.50  24.62  S  12.20  12.29  F  7.23  7.04  C  18.15  18.59  H  4.67  4.48  Sn  41.90  42.25  S  11.32  11.49  F  6.71  6.31  Sn  39.47  38.7  S  10.56  10.78  CI  23.35  23.09  6.26  5.96  F  - 56 -  reacted exothermically at -90° to produce insoluble i n the excess (CH^^Sn and  (CH^) SnS0 F, which was 3  3  CH^.  -90° (CH ) Sn 3  +  4  HS0 F  (CH ) SnS0 F  3  3  3  3  +  CH  4  The product was isolated by d i s t i l l i n g o f f the excess (CH ) Sn. 3  4  (CH ) SnS0 F i s a hygroscopic white s o l i d which melts without 3  3  3  decomposition at 108° and can be sublimed under vacuum at 70-75°. reaction also goes to completion, e.g. i n one preparation, 1.50  This  ml  (2.62 g, 26.1 mmoles) of HS0 F reacted with ( C H ^ S n to y i e l d 6.87 g 3  (26.1 mmoles) of (CH ) SnS0 F. 3  3  Trimethyltin fluorosulfate i s soluble  3  i n HS0 F and reacts with HS0 F to produce ( C H ) S n ( S 0 F ) , 3  3  3  yet another route to this compound.  2  3  providing  2  Elemental analysis results f o r  (CH ) SnS0 F are l i s t e d i n Table 12. 3  3  3  (CH ) SnS0 CF was prepared by Schmeisser i n a similar manner 3  3  3  3  and this method could be extended to the production of (CH ) SnS0 CH 3  from (CH ) Sn and HS0 CH at 15°. 3  4  3  Attempts to make  3  3  3  (CH ) SnS0 Cl 3  3  3  using HS0 C1 and the same method surprisingly yielded (CH ) SnS0 CH 3  3  as the sole product.  (CH ) Sn 3  4  3  3  The reaction scheme i s probably:  +  HS0 C1  *-  3  [(CH ) SnS0 Cl] 3  3  3  +  CH  [(CK) SnS0 Cl] 3  —*-  4  3  (CH ) SnS0 CH 3  3  3  +  3  CH  +  4  HC1  The product was i d e n t i f i e d as (CH ) SnS0 CH by elemental analysis 3  3  3  3  and comparison of the infrared and Mossbauer spectra with those of  3  3  - 57 (CH ^SnSO^Hg.  The melting point of (CH ) SnS0 CF 3  3  3  3  prepared here i s  76-78° i n good agreement with the previous report of 74-75°.  77  The  76 previously reported mp f o r (CH ) SnSC> F was > 100° 3  3  again i n  3  agreement with our r e s u l t s . 5.  (CH ) ClSnS0 F and CHgCl^SnSO F 3  2  3  Dimethylchlorotin fluorosulfate was prepared i n a ligand r e d i s t r i b u tion reaction when 0.492 g (1.42 mmoles) of ( C H ) S n ( S 0 F ) 3  with 0.311 g (1.42 mmoles) of ( C H ) S n C l 3  2  2  2  3  2  was reacted  i n dry chloroform at room  temperature f o r several hours i n a round bottomed f l a s k attached d i r e c t l y to a glass f r i t v i a a B24 ground glass union.  (CH ) Sn(S0 F) 3  2  3  +  2  (CH ) SnCl 3  2  — ^  2  2 (CH^ClSnSC^F  An excess of ( C H ) S n C l could also be used i n this reaction. 3  2  2  The  (CH ) ClSnS0 F i s insoluble i n CHC1 and could be isolated by f i l t r a t i o n 3  2  3  3  followed by washing with CHCl-j.  (CH ) Sn(S0 F) 3  2  3  2  i s also insoluble i n  CHC1 and could have been a contaminant i n the product, however, the 3  reaction went 100% to completion and no ( C H ) S n ( S 0 F ) was evident i n 3  2  3  2  the product. Methyldichlorotin fluorosulfate was prepared i n a similar reaction of CH ClSn(S0 F) 3  3  2  with C H ^ n C l ^  CH ClSn(S0 F) 3  3  2  +  CH SnCl 3  3  —>•  CH Cl SnS0 F 2  Both of these products are hygroscopic white s o l i d s .  Attempts to  - 58 -  prepare the analogous SO^CF^ derivatives by similar methods were a l l unsuccessful, as were attempts to prepare any of these derivatives by s o l v o l y s i s reactions.  (CH ) Sn(S0 F)(S0 CFp  6.  3  2  3  3  Mixed acid derivatives could be prepared by reacting a trimethyltin sulfonate with one of the other sulfonic acids.  Dimethyltin f l u o r o -  sulfate trifluoromethylsulfate was prepared i n t h i s manner by adding an excess of HS0 CF 3  box.  to (CH ) SnSC> F i n a two-part reactor i n the dry  3  3  3  3  Methane was released i n the reaction and the (CH ) Sn(SC> F) (S0 CF ) 3  was i s o l a t e d by removing the excess HS0 CF 3  (CH ) SnS0 F + HS0 CF 3  3  3  3  (CH ) Sn(S0 FX(S0 CF ) 3  2  3  3  3  3  by vacuum d i s t i l l a t i o n .  3  HSO CF - — ^  3  2  (CH^SnCSO^) ( S 0 C F ) 3  3  i s a hygroscopic white s o l i d with a decomposition  3  point of 315°. The elemental analysis results are Sn calc, 29.91; found, 30.26 and F calc, 19.15; found 18.86.  7.  CH Sn(S0 F) 3  3  3  Methyltin t r i s f l u o r o s u l f a t e i s the only member of the series of compounds described by the formula (CH„) CI Sn(SO.F). 3 x y 3 4-x-y r  J  not be prepared.  As already mentioned, i n one attempt to prepare  CH Sn(S0 F) , CH SnCl 3  3  3  which could  3  3  was heated to 140° i n the presence of HS0 F 3  i n order to replace the l a s t C l ~ by SO-jF , but only C l S n ( S 0 F ) -  2  isolated.  In another attempt CH ClSn(S0 F) 3  3  2  3  2  was  was reacted with  peroxydisulfuryl d i f l u o r i d e i n a small one-part reactor with a t e f l o n  3  - 59 -  stem stopcock. and  This reaction, as well as reactions of (CH^J^SnCl^  (CH„) SnCl with S.CvF., produced only Sn(SO.F).. 3 3 2. o 2. 3 H 0  Because S.0.F i s zbz o  an oxidizing agent and the substrates contained oxidizable methyl groups, only very small quantities  200 mg of substrate) were used  and the vessels were l e f t i n a safe place while the reactions proceeded. One of the several reactions of this type which were attempted did explode.  C.  Structural: Studies  1.  (CH ) Sn(S0 F) 3  2  3  2  Of these compound*, dimethyltin b i s f l u o r o s u l f a t e i s the most thoroughly  investigated and therefore i t can be used as a model for  discussion of the s t r u c t u r a l and bonding p o s s i b i l i t i e s of the others. The c r y s t a l structure of ( C H ) S n ( S 0 F ) , which has been 3  determined by X-ray d i f f r a c t i o n ,  2  135  3  2  i s s i m i l a r to that of (CH ) SnF 3  and consists of sheet-like polymers with two equivalent bridging S0 F groups. 3  2  25 2  bidentate  As shown i n Figure 9 the geometry at each t i n  i s octahedral with the methyl groups above and below the S n ( S 0 F ) . 3  plane, i . e . i n a trans octahedral arrangement about t i n . The  4  tin-carbon  bond lengths are short and a l l three S-0 bonds are equivalent within experimental KS0 F.^ 3  l i m i t s and equal to the value of r  The Sn-0 bond i s longer than i s usually found for covalent  Sn-0 bonds, e.g. i n SnCl^-2SeOCl Sn-C  for the ionic  Sn-0  2  bond length and the equivalence  i s ^ 2.12  ° 18 A.  Both the short  of the S-0 bond lengths suggests 2+  that the c r y s t a l consists of (CH ) Sn 3  2  cations and S0 F 3  anions.  Other s t r u c t u r a l information, however i s inconsistent with this fomulation.  - 60 -  Figure 9  The Crystal Structure of (CH ) Sn(S0 F)* 3  2  3  One polymeric layer viev.'ed along a *  1  K2)  Bonddistances A  © Sn  © S  O o  ©  F *FH  o  Sn- C S n - O(l) S n - 0(2) S-OO) S - 0(2) S - 0(3) S-F  2 . 0 6 5 (9) 2 . 2 7 0 (6) 2 . 2 7 1 (7) 1 . 4 3 7 (8) 1 . 4 2 8 (7) 1 . 4 2 2 (11) T.504(8)  C Allen, d.A.Lerbscher and 3.Trotter. O.Chem. Soc. (A) 2507,(1971).  -  61 - -  Table  Reported  interatomic  Bond  d i s t a n c e s and s e l e c t e d bond  parameter*'  KSO^F'  "  angles  for  (CH^SnCSO  Rc „ S-F  [A]  1.58  1.50  Rg_0  [A]  1.43  1.42  R  2 x  13  Sn-0  [  l  ]  '  2  3  [&]  1.43  1.43  $  O-S-0  (av.)  112.9°  111.1°  *  0-S-F  (av.)  105.8°  106.4°  uncorrected  (av)  denotes  average  0'  denotes  the oxygen  for  thermal  atom bonded  F)2~"  0  Rs_Q,b)  denotes  some  motion  to both  S and Sn  fluorosulfates  - 62 -  Both the v i b r a t i o n a l spectra and  the conductivity  a more covalent interaction between the  (CH^^Sn and  results  the  SO^F.  The v i b r a t i o n a l results with an assignment of the peaks are i n Table 14.  The assignment of the nine SO^F  comparison of these spectra  indicate  listed  modes i s made by  to those of a large number of C  symmetry s  fluorosulfates^  9 , 7  ^ some of which are Raman spectra of l i q u i d s which  can be analysed more f u l l y by making use of p o l a r i z a b i l i t y measurements. The  infrared spectrum of (CH )_Sn(SO F) j  SO^F  j  /.  shows C  symmetry for  group (9 modes) with a large s p l i t t i n g of the previously  E symmetry SO^  stretching mode.  the  S  c.  degenerate  The s p l i t t i n g i s much larger than i s  found for i o n i c s a l t s whose symmetry i s reduced by c r y s t a l e f f e c t s , 64 NOSO^F, and  e.g.  i t s magnitude i s similar to the size of  s p l i t t i n g s found i n other covalent fluorosulfates. modes, v  5  c  The other two  E  and v, i n the i o n i c , are also s p l i t by large amounts b  compared to the s p l i t t i n g s found i n NOSO^F. stretching modes (1350, 1180  and  1080  cm"  1  The positions of the  vs. 1408,  for BrSO^F) are i n d i c a t i v e of bidentate SO^F bridging  the  and  1206  and  SO^  884  cm"  1  since bidentate  i s confirmed i n t h i s case these r e l a t i v e positions of v  SO^'s  can be used as a guide for assignment of the vibrations of other t i n fluorosulfates. Another i n d i c a t i o n of covalency i s the position of vS-F. ( C H ) S n ( S 0 F ) , vS^-F i s shifted from the p o s i t i o n of 3  2  3  2  found for ionic fluorosulfates  63  to the 800-900 cm  i s found i n covalent f l u o r o s u l f a t e s . ^  9  —1  750  In cm"  1  region where vS-F  The higher energy of  the  S-F bond i s consistent with the shortness of the S-F bond as shown by the c r y s t a l structure.  In the vSn-C region, mutual exclusion  of i r  - 63 -  Table 14.  V i b r a t i o n a l Spectra of (CH ) Sn(SO F)  IR Ccm") 1  Raman (c«*  Assignment  3048 m  V 3 H  2952 mw  2944 m  2860 vw  2871 m  V 3 H  2425 w 1455 mw 1350 vs,br  vS0  3  (A")  vS0  3  (A')  1088 s  VS0  3  (A*)  826  vS-F (A')  1354 s  1222 w 1180 vs,br 1088 m,sh 1072 s,br 827 m,sh  p(Sn)-CH  798 vs,br  3  650 w 620 m,sh  610  6S0 (A")  590 ms  584  6S0  551 mw,sh  v Sn-C a 6S0 (A')  3  576 s 554 ms  3  (A')  3  417 s  420 w  v Sn-C s PS0 (A")  360 w  367 mw  pS0 F (A')  304 w  320 mw  vSn-0  531 vs  2  3  s = strong  V  stretch  m = medium  <5  bend  w = weak  P  rock  br= broad  a  asymmetric  sh= shoulder  s  symmetric  - 64 -  and Raman peaks i s observed for the two  tiri^-carbon stretching modes  as expected for a linear C-Sn-C arrangement. Sn-C  The positions of the  vibrations are consistent with those of other octahedral  (CH^^Sn  compounds. The e l e c t r i c a l conductivity study on (CH ) Sn(SC> F) 3  2  3  2  i n HSO^F  shows the expected large increase i n conductivity when a fluorosulfate i s added, however, the increase i s only one-half as great as i s observed for the same concentrations  of KSC^F.  If ( C H ) S n ( S 0 F ) 3  2  3  2  were i o n i c , i t would be expected to dissociate completely i n HS0 F 3  and the increase i n conductivity should be twice that of KSC^F. The observed increase means that only approximately one-quarter of the S0 F groups i n (CH ) Sn(S0 F> 3  3  2  3  2  are dissociated to SC^F  therefore there must be considerable (CH ) Sn and SG^F 3  2  i n HSC^F and  covalent i n t e r a c t i o n between  to hold these units together i n solution.  The values of the Mossbauer parameters for ( C H ) S n ( S 0 F ) 3  isomer s h i f t (6), 1.82  2  mm/sec and quadrupole s p l i t t i n g  3  2  (A), 5.54  There i s also an appreciable room temperature e f f e c t , R = 0.089. isomer s h i f t and quadrupole s p l i t t i n g are exceptional.  5.54  i s the largest A known for t i n and 6 i s among the largest for compounds.  are mm/sec. The  mm/sec organotin  In order to explain these r e s u l t s a bonding scheme  which predicts a large s electron density at t i n i s needed to explain the high isomer  shift.  The s electron density must also be concentrated  along the z axis to produce a large e l e c t r i c f i e l d gradient and hence a large A.  - 66 -  Table 15.  K  E l e c t r i c a l Conductivity of (CH ) Sn(SO F ) i n HSC^F at 25°. 2  (ohm  cm  )  m  2.0 X 10"  3  7.0 x 10~  4  0.60  6.0 x 10"  3  4.2 x 10~  3  0.48  1.0 X 10"  2  8.8 x 10~  3  0.41  1.4 X l O "  2  1.47 x 10~  2  0.36  1.8 X l O "  2  2.12 x 10~  2  0.32  Table 16.  Mossbauer Data f o r (CH„) Sn(SO_X) 0  Compound  (CH ) Sn(S0 F) 3  2  3  2  (CH ) Sn(S0 CF ) 3  2  3  3  (CH ) Sn(S0 Cl) 3  2  3  2  3  2  2  (CH ) Sn(S0 CH ) 3  3  2  (CH ) Sn(S0 C H ) 3  2  3  2  5  2  (CH ) Sn(S0 C H CH ) 3  2  (CH ) SnF 3  2  3  6  90  (CH ) Sn(N0 ) 2  4  2  (CH_)„SnS0. 3 2 4 3  Y  3  2  3  2  6 (mm/sec)  A (mm/sec)  R  1.82  5.54  0.089  1.79  5.51  0.129  1.75  5.20  0.197  1.52  5.05  0.129  1.52  4.91  0.117  1.51  4.85  0.18  1.23  4.52  1.57  4.94  1.62  4.13  V  - 67 -  2.  Other methyltin sulfonates The v i b r a t i o n a l and MSssbauer results f o r (CH^)^SnCSO^F)^ can  now be used as a guide i n the investigation of the other methyltin sulfonates.  (a)  (CH ) Sn(S0 X) 3  2  3  2  A series of compounds with the general formula where X = F, C F  CI, CH ,  3>  (CH ) Sn(S0 X) 3  2  3  , and C^R^CU^ have been prepared.  3  MSssbauer parameters for these compounds are shown i n Table 16. 6  2  The Both  and A values - for this series f a l l into f a i r l y narrow ranges and a l l  compounds have noticeable room temperature e f f e c t s .  These s i m i l a r i t i e s  suggest common possibly polymeric structures f o r these compounds s i m i l a r to that of (CH > Sn(S0 F) . 3  2  3  The decrease i n both 6 and A  2  X changes from F through CF , CI, CH » and C ^ 3  as  to C^R^CH^ appears to  3  136 proceed p a r a l l e l to the decrease i n electronegativity of X  for  the same series. Infrared and when possible Raman spectra were recorded for the members of this series.  Because of experimental d i f f i c u l t i e s and  the more complex nature of some of the sulfonate groups, a complete analysis of the spectra could not be made. for the S0  3  However, the same pattern  stretching modes indicating bidentate sulfonates could be  seen i n a l l cases. The MSssbauer results and v i b r a t i o n a l frequencies i n the Sn-C region for the Me Sn derivatives of some oxyacids are l i s t e d i n 2  Table 18, and as i s shown i n the table the isomer s h i f t s vary from 1.03 mm/sec for ( C H ) S n ( ( C H ) 3  2  3  As 2  °2^2  t 0  1 , 5 1  m m  /  s e c  f o r  t h e  P  ara  toluene-  - 68 -  Table 17. V i b r a t i o n a l Frequencies of (CH )_Sn(SO X)  (CH ) Sn(S0 CF ) 3  2  IR  3  3  2  Raman  (CHg) Sn(S0 Cl) 2  3  £  (CH ) Sn(S0 CH > 3  2  3  3  Compounds.  2  (CH )^(SO^H^ 3  IR  IR  IR  Raman  1405 w  1340 s  1300 m  1314 w  1320 s,br  1240 s,br  1250 s,br  1260 w  1155  1160 s,br 1090 sh  1090 s,br  1200 s 1080 sh  1196 m  1036 s  1050 m 965 sh  1030 s ,br 975 m  1035 990 905 810 790 745  vS0 (A") 3  1324 1292 1231 1212 1195  s w s m vs  1325 1225  vS0 (A') 3  1150 s,br vS0 (A*) 3  1035 s 982 w 821 vs 774 mw 645 s 630 s 583 m  783 642 580  825 s 775 s 625 600 575 555  m s s s  804 s 778 s 591 w ,m 534 m  s w m s sh s  385 m,sh 370 ms 351 326 322  522 sh 383  514 m  512 s 480 sh  532 s 520 m  390 s  406 s 385 s  342 m  339 m  331 280 w 220  735 w  598 m 572 s 530 sh  531 vs 520 m,sh  935 w  2  - 69 -  Table 18. Dimethyltin Derivatives of Oxyacids.  Vibrational  MSssbauer  Compound  (mm/sec)  A (mm/sec)  R  IR (cm  Raman (cm  (CH ) Sn(C H P0 H)  2  1.34  4.57  0.26  590m'  522s.  (CH ) Sn(C H P0 H)  2  1.17  4.30  0.19  582nr  518s  1.23  3.72  0.16  573m,528m  575w,531s  1.23  4.35  0.10  580s  518s  1.15  3.36  0.23  573m,526w  572w,529s  1.06  3.20  0.23  572m,526w  579w,525s  1.06  3.10  0.18  573m,526w  572w,529s  1.03  3.73  0  580m  (CH ) SnC H 0 .(CH ) SnO  1.18  3.43  0.15  581m,527s  (CH ) SnC H 0 r  1.41  3.94  0  582m  (CH ) SnW0 -(CH ) SnO  1.17  3.17  0  572s,529w  566w,531s  (CH ) SnMo0  1.37  4.19  0.56  575s  534s  (CH ) SnC 0 .H 0 °  1.55  4.65  (CH ) SnW0  1.39  3.53  1.42  4.10  1.28  2.98  3  2  3  6  2  5  6  3  5  2  [(CH ) Sn] (P0 ) 3  2  2  4  (CH ) S (H P0 ) 3  2  n  2  2  2  2  [(CH ) Sn] (As0 ) 3  2  3  4  (CH ) SnC H As0 3  2  6  5  2  3  (CH ) SnC H CH As0 3  2  6  5  2  3  (CH ) Sn[(CH ) As0 ] 3  2  3  3  2  3  3  4  2  4  8  3  3  3  2  4  XJ  3  2  3  2  2  4  2  138 4  (CH ) SnMo0 3  2  138 4  (CH ) SnCr0 " ° LJ  3  2  2  2  4  4  2  2  4  4  2  2  4  582w,533s  - 70 -  sulfonate.  This v a r i a t i o n i s much larger than would be expected i f the  2+ same t i n containing ion, (CH^^Sn , existed i n a l l these compounds. 2For comparison the SnF ion has 6's ranging from -0.48 to -0.40 with b + + 137 2f i v e d i f f e r e n t cations from Na to C10„ and SnCl, has 6 from 2 6 +0.42 to +0.52 mm/sec with four d i f f e r e n t cation ranging from NH^"*" to NO . +  137  (b)  (CH ) SnS0 X 3  3  3  (CH ) SnS0 F, (CH ) SnS0 CF 3  3  3  3  3  3  3  and (CH ) SnS0 CH 3  white solids at room temperature.  3  3  3  are a l l hygroscopic  The geometries of these compounds,  to be consistent with ( C H ^ S n F , (CH > ^nClO^, the dimethyltin b i s 3  sulfonates, and other similar compounds, would be trigonal bipyramidal with planar CH Sn groups and a x i a l S0 X bridging groups forming linear 3  3  polymeric s o l i d s .  The infrared spectral frequencies which are l i s t e d  i n Table 19 confirm this expectation. This result disagrees with the report by Schmeisser who (CH ) SnS0 CF 3  3  3  77 3  claims that i r data, not reported, for  agree with spectra of i o n i c trifluoromethylsulfonates.  Looking f i r s t at the (CH ) SnS0 F spectrum, the nine fundamentals 3  3  3  expected for a fluorosulfate with C stretches are at 1335,  symmetry are observed and the S0  g  1200, and 1068 cm ^ i n very s i m i l a r positions  to the corresponding bands i n (CH > Sn(S0 F) .  The other six S0 F  modes also agree with those of (CH ) Sn(S0 F> .  They are the S-F  3  2  3  stretch at 820 cm \  S0  3  3  2  2  3  2  3  bending modes at 630, 596 and 578 cm ^ and  S0 F rocking and torsion modes at 410 and 370 cm ^. 3  Only one band i n  the 500-600 cm ^ region can be assigned to tin-carbon stretching modes.  This mode, v  Sn-C at 555 cm \ a  i s found i n the same p o s i t i o n  3  82 83 '  Table 19.  Vibrational Frequencies of (CH ) SnS0 X. 3  (CH ) SriSOgF 1408 w, 6 CH_ a 3 1355 s, vSO (A ) 11  1335 m, 6 CH s 3  3  3  (CH ) SnS0 CF 3  3  3  3  (CH ) SnS0 CH 3  3  3  3  1400 w, 6 CHL a 3 vs,br, vS0 (A") 1319  1418 w, 1405 w,sh 6 CH„ a 3 1345 m,sh, 1337 m, 6 CH„ s 3  1226 vs, vCF (E)  1266 s, vS0 (A")  3  Q  3  3  1254 vs,  1218 s, vS0 (A') 3  1179 s,br, vCF (A )  1196 v s  3  1  1207 vw, 1196 vw,  1123 w, 2 x 555  1145 s, vSO (A»)  1112 vs, vS0 (A')  1068 vs, vS0 (A')  1026 s,vS0  1035 s, vS0 (A')  3  3  (A')  3  3  968 w,  820 s,sh, vS-F (A') 778 vs, CH  rock  3  796 s, CH  810 s,sh, CH  rock  3  771 m, 'WS-C  (A ) 1  rock  3  793 s, vS-C  630 m, 6S0 (A )  633 ms, 6S0 (A")  562 s, 6S0 (A')  596 s, 6S0 (A')  577 ms, 6CF (E)  550 vs, v Sn-C a 531 s, 5S0 (A')  M  3  3  3  3  578 s, 6S0 (A')  3  3  555 s, v Sn-C a  555 s, v Sn-C ' a 530 m,sh, 6S0 (A')  516 ms, 6S0 (A')  517 ms, 6S0 (A')  352 m,sh  3  3  3  356 ms, S0 CF 3  3  3  425 mw,  3  3  317 m, vSn-0  2  3  S0„CH rock (A") 3 3 o  rock  347 s, ^<5CF (A ) 330 m, S0 CF  298 ms, vSn-0  3  346 m,  410 ms, S0 F rock (A") 370 m,br, S0 F rock (A')  3  330 m, vSn-0  rock 275 m,sh,  S0 CH 2  3  rock (A*)  - 72 118 as i t i s i n other similar five-coordinate t r i m e t h y l t i n compounds. There are no IR peaks i n the 520 cm stretch would be expected.  1  region where the symmetric  The absence of v Sn-C i n the infrared i s s  consistent with a t r i g o n a l bipyramidal geometry because f o r  only  the asymmetric stretch would be IR active. Both tin-carbon stretches should be Raman active but Raman spectra could not be obtained. The infrared spectrum of (CH^) .jSnSO^CF^ ± e a s i l y assigned s n  o  t  a  s  as the spectrum of (CH^)^SnSO^F i s because the SO^ and CF^ modes are found i n the same s p e c t r a l regions.  This i s p a r t i c u l a r l y obvious f o r  i o n i c trifluoromethanesulfonates where the symmetries of both of these components are the same and extensive coupling r e s u l t s .  It i s  therefore not surprising that two independent studies, both using normal coordinate analysis and extensive comparison to SO^CH^ , S0 CD 3  3  and S0 CC1 3  arrive at d i f f e r e n t assignments f o r S0 CF .  3  3  However, f o r the covalent S0 CF 3  3  3  group found here, the symmetry of  some of the S0 modes w i l l be reduced and this should lead to a 3  clearer d i s t i n c t i o n between the S0 and CF modes. 3  Tentative assignment  3  of a l l peaks i n the infrared spectrum of (CH ) SnS0 CF 3  using the (CH ) SnS0 F spectrum as a guide. 3  S0 CF 3  3  3  3  group are found >at approximately  corresponding  3  3  3  has been made  V i b r a t i o n a l modes f o r the  40 cm  1  lower energy than the  S0 F modes as found e a r l i e r for the pairs CF S0 F and 3  3  2  139 FS0 F and CF S0 C1 and FS0 C1. 2  3  2  As i n the fluorosulfate, only the  2  asymmetric tin-carbon stretch i s evident i n the IR and not the symmetric s t r e t c h . The spectrum of (CH ) SnS0 CH 3  3  3  3  can be s i m i l a r l y assigned.  It i s  i n t e r e s t i n g that a duplication of a l l CH modes i s observed here, as i s 3  - 73 expected with two d i f f e r e n t CH^ groups i n the molecule. The results of the Mossbauer spectra are shown i n Table 20 along with values f o r some similar compounds.  No room temperature  effect  i s observed f o r any of the trimethyltin sulfonates indicating perhaps weaker polymeric association than i s found i n the corresponding dimethyltin derivatives.  This absence does not rule out the p o s s i b i l i t y  of polymeric association altogether.  The isomer s h i f t s of the sulfonates,  i n the narrow range of 1.43 to 1.52 mm/sec are among the highest reported f o r (CH^^SnClV) compounds and the quadrupole s p l i t t i n g s are 98 also among the largest known, larger than haloacetates for example. A  140 or sulfates  As was found for the dimethyltin bissulfonates, both <5 and  decrease with decreasing electronegativity of X. The behaviour of ( C H ^ S n S O ^ i n HS0 F i s of interest i n view 3  of previous reports of a solvated (CH^^Sn"*" cation i n H^SO^."^  The  3  p l o t of s p e c i f i c conductance vs. molality, shown i n Figure 12, indicates f a r smaller conductance values than would be expected f o r a 1:1 e l e c t r o l y t e .  The observed behaviour i n solution suggests that  there i s incomplete breakdown of the polymers into ions. At higher concentrations the d i s s o c i a t i o n decreases further and some s o l v o l y s i s of the tin-carbon bonds accompanied by CH^ release occurs to give dimethyltin b i s f l u o r o s u l f a t e . into ( C H ) S n ( S 0 F ) 3  2  3  i n HS0 F according to:  2  3  (CH ) SnS0 F 3  3  The quantitative conversion of (CH^J^SnSO^F  3  i s e a s i l y accomplished  +  HS0 F 3  — ^  (CH^SnCSO^  i n more concentrated solutions.  +  CH  4  It must be  concluded that, i n contrast to the findings i n H.SO., the stronger  Table •^^Sn  Mbssbauer Data  20  f o r (CH-)3Sn(IV)  Compound  Compounds a t  S (nan/sec)  80 K  /\(mm/sec)  (CK3)3SnS03F  1.52  4.61  ('cH3)3SnS030P3  1.52  4.57  (CH3)3£nS03CH  1.43  4.21  1.47  4.75  1.38  4.22  1.37  4.06  1.18  3.47  3  (CH3)3SnSb?6 (CH3)3SnC02C? (CH3)3Sn (CH3)S;iP  2  S 0  3  9 3  4  1 4  °  1 4 1  F i g u r e 11 " s n M O S S B A U E R S P E C T R U M of (CH ) SnS0 CH 3  3  —i -6  3  1  3  at 8 0 ° K  1 -3  1  1  O  1  1 3  D O P P L E R V E L O C I T Y ( mm / s )  >  r 6  - 75 -  Table 21 S p e c i f i c E l e c t r i c Conductance of (CH > SnS0 F and ( C H ^ S n ( S 0 F ) 3  3  3  2  in  3  HS0 F at 25°C 3  (CH ) SnS0 F 3  [  moles  2.5x10  -3  3  (CH ) SnS0 F  c  3  3  -4  4.65x10  -4  -4 11.22x10  10.64x10  -2 1.0x10  -4 14.20x10  13.30x10  1.25x10  -4 17.01x10  -4 15.74x10  measured immediately a f t e r a d d i t i o n measured a f t e r 30 minutes.  3  3  3  2  4.15x10  -4  6.18::10  7.80x10  -3  7.5x10  (CH ) Sn(S0 F)  ohm-1 cm-1  CE-1  8.26x10  5. u x i O  3  ohm-1  [ohai-l cm-1  4.82x10  3  -A  -4  8.75x10  -4  -4 10.50x10 12.40x10  - 76 -  - 77 -  protonic acid HSO^F i s not suited to the formation of ( C H ) S n ( s o l v ) +  3  3  v i a a simple s o l v o l y s i s . (c) CH ClSn(S0 X) , C H ^ l ^ n S C ^ F 3  3  2  and (CH ) ClSnS0 F 3  2  3  The results of the v i b r a t i o n a l spectra of CH ClSn(S0 F) , 3  3  2  CH ClSn(S0 CF ) , CH Cl SnSC> F and (CH ) ClSnS0 F are l i s t e d i n Table 3  3  22.  3  2  3  2  3  3  2  3  In a l l cases the position of the S0 X v i b r a t i o n a l modes agree 3  with those of the corresponding (CH^SnSC^X and (CH > Sn(S0 X) 3  2  3  spectra  2  indicating that these compounds also have bidentate SO^K groups. This would lead to hexa-coordination for CH ClSn(S0 X) , most l i k e l y 3  3  2  with the methyl and chlorine groups above and below the S n ( S X ) n  3  plane.  In CH Cl SnS0 F 3  2  3  2  both the asymmetric and symmetric tin-chlorine  stretches are observed i n both the IR and Raman indicating a non-linear SnCl  arrangement.  2  The same r e s u l t i s found f o r C,,Sn i n (CH ) ClSnS0 F. 3  2  3  The structures of these two compounds w i l l l i k e l y be t r i g o n a l bipyramidal with a x i a l S0 F groups and t r i g o n a l planar (CH ) ClSn 3  groups f o r (CH^ClSnSO^F  3  2  and C l ^ C l ^ n group for CH Cl SnS0 F 3  2  3  i n the  equatorial plane, resulting i n polymers much l i k e those suggested for (CH ) SnS0 F, however, as indicated by the molecular structure of 3  3  3  (CH ) SnCl 3  2  2  (Figure 1) chlorine bridging i s also possible.  The Mdssbauer parameters of these four compounds are l i s t e d i n Table 23 and the magnitudes of these parameters are consistent with the  geometrical arrangements suggested.  They c e r t a i n l y unambiguously  indicate the presence of true compounds rather than reactant mixtures.  Table 22. V i b r a t i o n a l Spectra of (CH„) CI Sn(SOoX). 3 x y -? 4-x-y Assignment  CH ClSn(S0 F) 3  IR 5. CH a 3 vS0 (A ) Q  M  3  3  2  Raman  CH C1 SnS0 F 3  2  IR  1440 m  1405 vw  1361 s  1350s  3  Raman  (CH ) ClSnS0 F 3  2  IR  1360w  vCF (E)  1195 s  vCF (A)  1155 s,sh 1022 s  vSO (A') vS0 (A')  1095 s 1065 sh  1080 m  1072 s  830 s,sh  825 m,sh  820 m,sh  812,vs,br  806 vs,br  795 vs,br  1400 w  1074 w 825 w  640 vw 623 m  605 ms  6S0  3  590 s,sh  603 w  588 s  v Sn-C a vSn-C  578 s  585 m  576 vs  6S0  555 s  562 m  555 ms  3  610 w  560  v Sn-C s PSO  3  v Sn-Cl a vSn-Cl v Sn-Cl s PS0,F  420 m  423 m  405 w  405 w  385 ms  390 s  384 s  387 sh  305 mw  308 mw 250 m  368 s  300 w  305 w 247 w  3  3  3  3  816 ms  PCH  774 m,sh  vS-C  640 sh  6S0  3  3  3 1  »  607 s  603 w  628 m  6S0  590 m  594 w  585 m  5CF (E)  578 m  582 m  575 m  vSn-C  555 s  562 m  518 m,sh  6S0  527 m  535 s  510 s  6CF (A)  409 m  416 w  375 s  vSn-Cl  362 s  PS0CF (A")  350 m,sh  vSn-0  325 mw  PS0 CF (A')  345 m 366 s  IR  1228 s, sh  1072 s  610 m,sh  Assignment  1213 w  vS0 (A')  3  2  1220 sh 1190 s,br  6S0  3  1320 s,br  1250 m  3  3  1320 w  1250 vs ,br  PCH  3  1343 s  1165 vs,br  vSF  CH ClSn(S0 CF )  6 CH„ a 3 vS0 (A")  1220 sh  o  Raman  1403 w  6 CH_ s 3 vS0 (A') 3  3  345 m 306 m  322 mw  3  3  3  3  3  3  - 79 -  Table 23.  Mossbauer Data for (CH„) CI Sn(SO X)  Compound  6 (mm/sec)  CH ClSn(S0 F) 3  3  2  CH ClSn(S0 CF ) 3  3  3  2  CH Cl SnS0 F 3  2  3  (CH ) ClSnS0 F 3  2  3  D.  Discussion  1.  Syntheses  R  A (mm/sec)  1.23  3.77  0.12  1.19  3..70  0.20  1.14  3.25  0.55  1.58  4.69  0.05  An extensive series of methyltin fluorosulfates could be  prepared  using one of two simple and v e r s a t i l e preparative routes; s o l v o l y s i s of  a methyltin substrate i n HS0 F or ligand r e d i s t r i b u t i o n reactions 3  of two methyltin compounds. by either method.  In some cases a compound could be made  The s o l v o l y s i s route could be extended to the  preparation of other methyltin sulfonates by substituting the appropriate sulfonic acids for HS0 F.  (CH^SnSO^, (CH ) Sn(S0 F)  3  3  2  CH SnS0 F were prepared by acid s o l v o l y s i s and 3  3  and CH Cl SnS0 F by ligand r e d i s t r i b u t i o n . 3  2  3  3  3  (CH ) SnS0 F, ( C H ^ C l S n S O ^ 3  3  3  24.  (CH ) SnS0 CF , ( C H ) S n ( S 0 C F ) 3  and  2  These reactions are  3  summarized i n Table  3  3  2  3  3  2  and C H C l S n ( S 0 C F ) 3  3  3  2  could be  prepared by s o l v o l y s i s reactions i n HS0 CF , analogous to those i n 3  3  HS0 F, but ligand r e d i s t r i b u t i o n reactions using these 3  trifluoro-  methanesulfonates as substrates and similar experimental were a l l t o t a l l y unsuccessful.  conditions  This lack of success i s possibly  - 80 -  Table 24.  Preparative Routes to (CH„) Gl Sn(SO.F), 3 x y 3 4-x-y  Solvolysis Reactions 1.  ex(CH ) Sn  2.  (CH ) Sn  3.  (CH ) SnCl  4.  (CH ) SnCl  5.  CH SnCl  6.  (CH ) SnS0 F  3  3  +  4  3  3  2  3  "  9  °*  0  +  exHS0 F  2  exHS0 F  +  3  2  *>  *-  exHSO F  2  CH  +  2  (CH ) S n ( S 0 F )  2 5  —  3  3  3  3  exHS0 F  +  (CH > Sn(S0 F)  \  5  3  +  2  (CH ) SnSOgF  >-  2 5  3  +  3  HSO F  exHS0 F  3  3  3  +  4  2  CH ClSn(S0 F) 3  3  2CH  +  2  (CHj) Sn(S0 F)  -»»  2 5  3  3  2  2  +  (CH ) Sn(S0 F) 3  2  4  3  4  HC1  +  +  2HC1  2HC1  +  2  CH  Ligand Redistribution Reactions 7.  (CH ) Sn(S0 F)  8.  Sn(S0 F)  9.  (CH ) Sn(S0 F)  10.  3  2  3  3  3  +  4  2  3  3  +  ex(CH > Sn 3  ex(CH ) Sn 3  3  CH ClSn(S0 F)  2  2  +  2  +  2 5  4  —  2 5  4  2  exCH SnCl 3  3  (CH  ^SnSOjF  (CH^SnSC^F  ex(CH ) SnCl 3  »•  2  cHCl^  CHC1*  (CH > ClSnS0 F 3  2  3  CH Cl SnS0 F 3  2  3  4  CH  4  - 81 caused by s t e r l c a l hindrance exerted by the bulky CF^ groups. Several general comments can be made about the systematic synthetic study of the s o l v o l y s i s of methyltin compounds i n HSO^F and ligand r e d i s t r i b u t i o n reactions of these compounds. (1)  Only mono- or d i s u b s t i t u t i o n i s observed, and  (2)  chlorine i s cleaved i n preference to carbon.  (3)  The s o l v o l y s i s reactions are simple clearcut reactions leading  to single products. (4)  Ligand r e d i s t r i b u t i o n reactions can be used to synthesize  compounds which could not be prepared by acid s o l v o l y s i s as well as to prepare some compounds which could also be made by s o l v o l y s i s . The s o l v o l y s i s reactions of methyltin compounds i n HSO^F are similar i n some respects to the s o l v o l y s i s reactions of the same 142 compounds i n anhydrous hydrogen f l u o r i d e , systems d i f f e r i n many respects.  however, these two  The main s i m i l a r i t i e s are that i n  both cases reactions occurred with a l l ( C H ^ ^ S n C l ^ ^ ^  compounds (n > 1)  to form a variety of compounds and i n a l l cases tin-chlorine bonds were cleaved before tin-carbon bonds were attacked.  In the HF  study i t was possible to control the course of the reaction by a l t e r i n g the reaction conditions such as time, temperature or mole ratios much more e f f e c t i v e l y than i t was i n the HSO^F study.  I t was also  possible to prepare CH^SnF^ but CH^SnCSO^F)^ was not obtained. Solvolysis reactions i n HSO^F could also be used to make other d i a l k y l t i n b i s f luorosulf ates using  (C2H,.)  ^SnCl or  other a l k y l t i n chlorides i n place of (CH^^SnCl.  (C2H^) SnCl2 3  or  Diethyltin bisfluoro-  sulfate and d i p r o p y l t i n b i s f l u o r o s u l f a t e were prepared i n this manner  - 82 but w i l l not be discussed here.  D i a l k y l t i n b i s f l u o r o s u l f a t e s and  d i a l k y l t i n bistrifluoromethanesulfonates have been investigated i n 143 conjunction with J.R.  D a l z i e l i n our laboratory.  The  solvolysis  method can also be extended to the s o l v o l y s i s of a l k y l t i n compounds 143 i n other strong monobasic acids such as HPO2F2.  Mossbauer r e s u l t s  for these derivatives as well as those of d i a l k y l t i n d i f l u o r i d e s are shown i n Figure 13 i n order to demonstrate the s i m i l a r i t i e s between these derivatives and the trends within the s e r i e s . detailed discussion see reference (CH ) Sn(S0 F) 3  2  3  2  For a more  143.  and CsSC^F were mixed i n HSC^F i n an attempt to 2-  prepare C s ( C H ) S n ( S 0 F ) , i n analogy to the ( C H ^ S n C l ^ 2  3  2  3  but no reaction occurred and only mixtures of CsS0 F and 3  were i s o l a t e d .  NOS0 F and 3  2.  2  (CH )2Sn(S0 F)^ 3  3  In a similar attempt, t h i s time to prepare  ( N O ) 2 ( C H ) S n ( S 0 F ) 2 C l 2 , N0C1 was 3  salts,  4  3  reacted with (CH > Sn(S0 F) , but  ( C H 3 ) 2 S n C l 2 were the only products  3  2  3  2  identified.  Spectra The v i b r a t i o n a l spectra of methyltin f l u o r o s u l f a t e s indicate that  the f l u o r o s u l f a t e groups are a l l bidentate and as shown i n Table 25,  the  nine fundamental SO-^F bands f o r a l l these compounds are i n very s i m i l a r positions. By making use of group theory p r e d i c i t i o n s on the presence or absence of v i b r a t i o n a l modes i n the Raman and infrared, the v i b r a t i o n a l spectra can be used to help predict the geometries of the methyltin fluorosulfates.  As shown i n Table 26 the tin-carbon stretching  frequencies i n the 620-520 cm ^ region show mutual exclusion for  - 83 Figure  13  COMPARISON OF  OF  DiALKYLTIN  MOSSBAUER (iv)  PARAMETERS  DIFLUORIDES,  BIS — D l -  FLUOROPHOSPHATES, BIS-FLUOROSULPHA TES  AND  NATES.  BIS—  -  TRIFLUOROMETHYLSULPHO-  Tabic 25  Vibrational modes of the'S0_F group,n various Cor.-ound  VS0(A") vSO (A') vso0 3  3  t i n and methyltin(IV) fluorosulfates  vSF SS0F(A) 6S0F(A") SSO^A') ?  3  3  S0 rock 2  (CH)Sn(S0F)  1350  1180  1076  827  620  590  554  417  (CH)Sn(S0F)  1355  1207  1068  820  630  596 '  555  410  (CK)SnC£(S0F)  1343  1190  1072  820  607  590  555  409  CHSnCi(S0F)  1361  1165  1072  830  620  590  555  420  Cr^Sntt (SO F)  1350  1250  1080  825  605  588  555  405  3 2  3 3  3  3  3 2  3  2  3  3  2  - 85 -  Tabic 2 6 Tin-carbon and l i n - c h l o r i n e s t r e t c h i n g  tr-odes i n the  me11:y 11 i.n(IV) chloro-sulfonnte compounds.  VSn-C  Compound  3  2  3  IR (CH ) Sn(S0 CF ) 3  2  3  3  3  3  IR CH SnC£ S0 F 3  2  2  3  (CH )SnC£(S0 F) 3  3  2  (CH )SnCUS0 CF ) 3  523 576  RA  3  (Ch* ) SnCUS0 F) 3  580  RA  2 )  3  3  3  2  Sn-C  530  IR (Ch* ) SnS0 F  v  sym  58^  RA  2  x>S:\-CZ V Sn-C£ a  531  RA  2  V Sn-C sym  576  IR (CH ) Sn(S0 F)  V Sn-C  IR  578  527  345  RA  582  535  345  IR  578  385  RA  585  390  IR  575  384  384  366  3S7  368  - 86 -  (CH ) Sn(SO F)  as expected for C-Sn-C, and absence of v  Sn-C i n the  IR for (CH^^SnSO^F i n d i c a t i n g a t r i g o n a l planar C^Sn moiety, but both asymmetric and symmetric Sn-C stretching modes are found i n IR and Raman f o r (CH^)2ClSnS0 F so t h i s molecule has a nonlinear 3  arrangement.  Similar bent C^Sn  (CH^^Sn  grouping i s expected f o r  CH^C^SnSO^F which also has both asymmetric and symmetric Sn-Cl stretches active i n both the IR and Raman spectra. The Mossbauer isomer s h i f t , quadrupole s p l i t t i n g s and room temperature e f f e c t s are best explained i f the f l u o r o s u l f a t e s are a l l bridging, i . e . i f octahedral structures occur for both (CH^)2Sn(S0.jF)2 and CH^ClSnCSO^F)2 and t r i g o n a l bipyramidal groups f o r (CH^SnSC^F, (CH^ClSnSC^F  structures with a x i a l  and CH^C^SnSC^F.  SO^F  These  polymeric f i v e - and six-coordinated structures are needed to explain the large quadrupole s p l i t t i n g s observed for a l l these compounds and to explain the room temperature e f f e c t s . Both the isomer s h i f t and the quadrupole s p l i t t i n g decreases i n the ( C H ) S n ( S 0 X ) 3  2  3  C„H , or C-H.CH„. C  2  series as f l u o r i n e i s replaced by C F  3>  CI,  CH , 3  These r e s u l t s are explained by considering the  withdrawal of p electron density around t i n by the electronegative S0 X 3  groups.  The smaller electronegativity of the S0 3 C1 groups f o r example  w i l l cause less withdrawal of electron density, more shielding of the t i n s electrons and therefore a smaller isomer s h i f t . electronegativity difference between SO^Cl and CH and CH  3  s u l f ate.  3  The smaller  than between SC^F  r e s u l t s i n a smaller A for the chlorosulfate than the f l u o r o Similar electronegativity e f f e c t s cause an analogous trend  i n the (CH^SnSC^X s e r i e s .  - 87 -  3.  Bonding Dimethyltin b i s f l u o r o s u l f a t e w i l l be used as an example i n the  discussion of the proposed bonding scheme because interatomic distances are available and can supplement v i b r a t i o n a l and Mossbauer data. 135 The structure of (CH^^SnCSO^F^j  as shown previously i n  Figure 9 suggests two dimensional sheet-like polymers with only van der Waals interactions between the various sheets. convenient  It w i l l be  to discuss three d i s t i n c t segments of the molecule;  (1) the l i n e a r C-Sn-C moiety with very short Sn-C bonds using 119 the X-ray structure, the v i b r a t i o n a l spectra and the  Sn Mossbauer  data as suitable probes into the bonding, (2) the distorted tetrahedral SO^F  groups using the s t r u c t u r a l  data as well as the v i b r a t i o n a l spectra, i n p a r t i c u l a r the removal of degeneracy of the E modes, and (3) the i n t e r a c t i o n between the two segments as reflected i n 119 the observed Sn-0 distances, the and the room temperature e f f e c t .  Sn Mossbauer quadrupole s p l i t t i n g s A s i m p l i f i e d model as shown i n  Figure 14, with the z axis along the C-Sn-C bonds and the four oxygen atoms i n the equatorial plane around t i n placed on the p o s i t i v e and negative branches of the x and y axes i s h e l p f u l . The high isomer s h i f t and short Sn-C bond distances indicate an e x t r a o r d i n a r i l y high s-character i n the tin-carbon bonds and therefore a high 5s electron density around t i n .  These results  suggest a sp^ hybrid o r b i t a l i s u t i l i z e d i n the bonding. A rather surprising departure from the previously discussed acetate structures  33 34 ' i s noted for the f l u o r o s u l f a t e group. A l l  - 88 -  Figure  14  Structural Features of (CH ) Sn 3  2  (S0 F)  i i  All bond distances are uncorrected  3  2  - 89 -  three S-0 bond distances are i d e n t i c a l within the l i m i t s of error and the nonbonded sulfur-oxygen distance i s not shorter as found for 33 the C-0 bonds of t r i b e n z y l t i n acetate. The S-0 distances are 65 i d e n t i c a l to those found f o r KSO^F and apparently only the S-F bond i s shortened.  These results are also confirmed by the v i b r a t i o n a l 47  spectra.  The average S-0 stretching frequency  i s i d e n t i c a l for KS0 F and 3  t i n compound. E symmetry S0  (CH ) Sn(S0 F) 3  2  3  2>  using Lehman's Rule  but vS-F i s raised i n the  There i s , however, a substantial s p l i t t i n g of the 3  stretching mode by vL70 cm ^ i n ( C H ) S n ( S 0 F ) . 3  2  3  2  Bonding i n tetrahedral sulfur compounds i s best described using 144 models involving i piT-dTr bonding proposed by Cruickshank. Using 144 145 a r e l a t i o n s h i p between bond distances and IT bond order  '  (see  Figure 16) a IT bond order of between 0.5 and 0.6 per S-0 bond seems logical.  In addition a survey of S-F bond distances indicates that  ir back donation into 3d o r b i t a l s on sulfur also takes place here.  As  a consequence one can postulate that e l e c t r o n i c charge removed from the (CH ) Sn region and r e s i d u a l lone pairs on the nonbonding oxygen 3  2  and on f l u o r i n e are used i n strong back donation. The i n t e r a c t i o n between the electron withdrawing S0 F groups and 3  the p o s i t i v e (CH ) Sn groups involves? P 3  2  bonding o r b i t a l s .  x  and p^ o r b i t a l s on t i n as  The electron density i n the Sn-0 region results i n  four i d e n t i c a l Sn-0  distances which are s l i g h t l y longer than those  observed previously.  Previously reported Sn-0  distances are a l l  ° 2 80 around 2.10  A, '  e.g. i n SnCl^.2SeOCl  2  the Sn-0 bond length i s  ° 18 2.12  A.  The resulting electron imbalance around t i n due to the high  electron density i n the z d i r e c t i o n and low density i n the xy plane i s  - 90 -  F i g u r e 15  P77-—d77 Bonding in Fluorosulphates  0.0  0.2  0.4  0.6  0.8  1.0  77--bond orders.  - 91 -  reflected i n the extremely large quadrupole s p l i t t i n g s for (CH^^SnCSO^F^ and the other dimethyltin bissulfonates. (CH^^Sn moiety and the SO^F  The i n t e r a c t i o n between the  groups can be described using a three  center four electron approach involving p^ and p^ o r b i t a l s on t i n , " ' '  1 1  thus avoiding any necessity to use 5d o r b i t a l contributions to o bonding. This view may  serve as an a l t e r n a t i v e to the often invoked rehybridiza-  3,2 „ 40 tion of sp d according to Bent. The noted s i m i l a r i t i e s between the interatomic distances of KSO^F and those of (CH^^SnCSO^F^ may the bonding.  give r i s e to an alternative view of  (CH^)2Sn(S0 F)^ can be viewed as consisting of t i g h t l y 3  2+ packed linear (CH^^Sn  cations and tetrahedral SO^F  i n a most economical fashion.  anions arranged  Although this s i t u a t i o n appears to be  closely approached i n (CH^^SnCSO^F^ and i t s SO^CF^ analogue, the chemical evidence (Sn-0 distances, room temperature effect and s p l i t t i n g of E modes) points towards strong covalent interactions. A s i m i l a r model based on a t r i g o n a l bipyramidal structure can be invoked for (CH^)^SnSO^F.  This compound w i l l have the three methyl 2  groups i n the xy plane bonded to t i n using sp  'hybridization at t i n ,  and the two oxygen atoms i n the a x i a l positions of the t r i g o n a l bipyramid bonded to t i n using the p electron bond.  As with  z  o r b i t a l on t i n and a three center four  (CH^)2Sn(S0 F)^ the Mossbauer and v i b r a t i o n a l 3  results are consistent with this model.  Both 6 and A are among the  very highest for t r i m e t h y l t i n compounds, and large s p l i t t i n g s of the E modes and energy increase for vS-F are observed i n the v i b r a t i o n a l spectra. As shown, these bonding models can be used to explain the X-ray s t r u c t u r a l data for (CH^^SnCSO^F^ and Mossbauer and v i b r a t i o n a l  Figure  17  Structural Features of Trimethyltin ( i v ) fluorosulf ate  z  I  - 93 -  r e s u l t s for ( C H ) S n ( S 0 F ) 3  2  3  and  2  (CH ) SnS0 F. 3  3  3  The other experimental  results also f i t i n with these models. (1)  The only p a r t i a l d i s s o c i a t i o n of ( C H ) S n ( S 0 F ) 3  2  3  and  2  (CH ) SnS0 F into ions i n HSC^F solution i s consistent with a formula3  3  3  tion involving considerable covalent interaction. (2)  The wide range of isomer s h i f t s and quadrupole s p l i t t i n g s for  oxyacid derivatives of dimethyltin(IV) also indicates covalency because, i f these compounds were i o n i c , changes i n the anion should only cause minor changes i n the electronic environment of  the  2+ (CH ) Sn 3  cation.  2  (3)  Increasing the acceptor a b i l i t y of the t i n atom by  CI, Br or SO^F  for one or both of the methyl groups w i l l increase the  covalency of the interaction between the t i n and the provided the s t r u c t u r a l framework i s maintained. inorganic  substituting  The  fluorosulfates Cl Sn(SC> F) , B r S n ( S 0 F ) 2  discussed i n the next chapter.  3  2  2  3  fluorosulfate  2  resulting  and  SnCSC^F)^ are  These changes have the following  on the Mbssbauer and v i b r a t i o n a l spectra; both the isomer s h i f t quadrupole s p l i t t i n g decreases and  substituents  are placed  the covalency of the S0 F group, r e f l e c t e d i n the E mode 3  splittings, (4)  and  the magnitude of the room tempera-  ture e f f e c t increases as more electronegative on t i n and  effects  increases.  Increasing the donor a b i l i t y of the acid group by  replacing  the fluorine i n SC^F by less electronegative substituents on s u l f u r such as CF„, CI, CH„, C„H_, or C^H.CH„ also increases the amount of 3 3 2 5 6 4 3 covalent interaction between the sulfonate and t i n as indicated decreases i n 6 and A and increased room temperature effects for  by  - 94 (CH ) Sn(S0 CF ) 3  2  3  3  (CH^Sn'CSC^Cl)  2>  2>  etc.  Similar e f f e c t s are also  seen f o r the (CH ) S n derivatives of weaker acids. 0  - 95 -  CHAPTER IV INORGANIC TIN FLUOROSULFATES A.  Introduction Many metal fluorosulfates have been reported over the years, and  the synthetic routes to these compounds have been discussed e a r l i e r . Although many binary fluorosulfates of formula MCSO^F)^ are known, almost a l l of these are mono, b i s or t r i s f l u o r o s u l f a t e s . I  The only 62  previous examples of tetraJc .isf luorosulf ates are CCSO^F)^ unstable at room temperature and SiCSO^F)^ 2CH.jCN tion by two coordinated ligands can be assumed.  which i s  i n which s t a b i l i z a -  Neither of these  compounds i s well characterized. The only inorganic t i n fluorosulfates to be reported are ClSn(SO„F)„ 3  prepared by the reaction of S O,F„ with anhydrous SnCl. n  2 o 2  3  H  below 100° and a product of the very approximate composition 59 Cl Sn(S0 F) ~Cl SnS0 F formed i n the slow i n t e r a c t i o n of SnCl^ with HS0„F at elevated temperatures. Since S„0..F doesn't decompose i n 3 2 6 2 glass vessels above 100° except f o r the reversible d i s s o c i a t i o n into 146 •S0 F radicals and a small amount of i n t e r a c t i o n with the glass 2  3  2  3  3  o  3  walls, further heating of ClSn(S0„F)„ with S„0,.F,, should, providing the 3 3 2 o 2 resulting product i s s u f f i c i e n t l y stable, enable us to replace the l a s t chlorine by S0 F. 3  This was  found to be the case by Poh Bo Long  - 96 -  of  this lab who  f i r s t prepared SnCSO^F)^ by this method i n 1968.  The synthesis of SnCSO^F)^ and C l S n ( S 0 F ) 2  3  2  147  and their Mossbauer and  v i b r a t i o n a l spectra were f i r s t investigated by Poh Bo Long and 148 subsequently by myself,  however these compounds were not f u l l y  characterized at that time, their relationship, of  t i n was not immediately  investigated.  to other fluorosulfates  recognized and their chemistry was  not  Therefore, although the preparative procedures 147 148  and  Mossbauer and v i b r a t i o n a l spectra have been reported  '  they are  included b r i e f l y here for completeness and for comparison to some related preparations which were attempted l a t e r . B. 1.  Preparations Sn(S0 F) 3  4  As reported previously"' a mixture of SnCl^ and a 5-10 1  f o l d excess  of S„0^F„ reacted instantaneously at room temperature to form a white 2 o 2 s o l i d and chlorine gas.  If the chlorine, excess S 0 F„ and any other 2. o 2. v o l a t i l e byproducts were removed by d i s t i l l a t i o n to avoid formation of CISO-F or ClO-SO-F at higher temperatures, 3  2  fresh S„0.F added and 2 o / o  J  the r e s u l t i n g solution heated gradually to 120° further reaction occurred and a white s o l i d i d e n t i f i e d as t i n tetrafciisf luorosulf ate was  formed.  The o v e r a l l reaction scheme would be  SnCl. 4  +  2S 0,F. 2 6 2 o  120°  —  Sn(S0 F). 3 4 o  +  2C1„ 2  However, since S„0-F was present i n excess and reaction conditions were 2 o 2 149 similar to those used for the formation of CISO^F, i t s formation i s o  - 97 -  l i k e l y and was indeed observed.  Further oxidation may  then have given  r i s e to the formation of ClC^SOgF probably v i a the intermediate C10SQ 'F. 3  SnCSO^F)^ i s a nonvolatile hygroscopic white s o l i d which melts with decomposition at 217° and i s insoluble i n the polar solvent HSO^F.  The i d e n t i t y of the product was  of f l u o r i n e , t i n and sulfur.  checked by elemental analysis  Fluorine and sulfur were determined  by  Bernhardt Microanalytical Laboratories and t i n gravimetrically as SnC^."''"^  2.  The a n a l y t i c a l results are l i s t e d i n Table 27.  Cl Sn(S0 F) 2  3  2  When f i n e l y powdered Sn(S0 F) 3  4  or any reaction intermediate of the  composition CI Sn(SO„F), with n > 2 was mixed with an excess of n 3 4-n anhydrous SnCl^ at room temperature  and the r e s u l t i n g suspension  s t i r r e d for about 15 minutes; a reaction occurred with the uptake of one mole of SnCl^ per mole of Sn(SC> F) to form a product of composition 3  Cl Sn(S0 F) . 2  3  4  The Mossbauer spectrum of this compound indicates that -  2  there i s only one environment for t i n r u l i n g out possible formation of an SnCl^-Sn(S0 F) 3  adduct.  4  The reaction to form d i c h l o r o t i n b i s f l u o r o -  s u l f ate, similar to reactions discussed i n Chapter I I I , proceeded, according to  Sn(S0 F) 3  4  +  SnCl  4  »-  2Cl Sn(SC> F) 2  3  2  Sulfur and fluorine were again analyzed by Bernhardt. and t i n were determined by p r e c i p i t a t i n g SnS  2  Chlorine  from a hydrolyzed sample  - 98 Table 27.  A n a l y t i c a l Results.  Compound  mp  Elemental Analyses Element  Sn(S0 F) 3  217  4  Cl Sn(S0 F) 2  3  Br Sn(S0 F) 2  3  2  2  207  142-5  3  3  Found  F  14.75  14.90  Sn  23.05  23.0  S  24.90  24.65  CI  18.29  18.15  F  9.80  9.55  Sn  30.61  30.5  S  16.55  16.4  Br  33.53  33.84  7.97  7.84  Sn  24.90  25.17  CI  32.81  32.95  Sn  36.60  36.3  F  ClSn(S0 F)  Calculated  - 99 -  of Cl^SnCSO^F)^ on addition of I^S solution. filtered  The SnS2 solution was  and the f i l t r a t e was heated to b o i l i n g to remove excess I^S.  Chloride could then be determined by potentiometric t i t r a t i o n  of the  f i l t r a t e with AgNO^ and t i n gravimetrically as the oxide once the SnS was heated i n the presence of a i r to convert i t to SnG^-  This  a n a l y t i c a l procedure was necessary because simple p r e c i p i t a t i o n of SnC^ from the hydrolyzed sample and t i t r a t i o n  of the f i l t r a t e for CI  gave r e s u l t s for Sn and CI which were always about 10% low, possibly due to the formation of chlorotin anions i n solution.  3.  Cl SnS0 F 3  3  T r i c h l o r o t i n fluorosulfate was produced when an excess of anhydrous SnCl. was reacted with S-0,,F at room temperature. 42 o 2 SnCl. 4  +  1/2S O F 2 6 2  -  Cl-SnSO.F J J  +  1/2C1„ z  This reaction i s exothermic (on one occasion the reaction mixture exploded rather unexpectedly) and the Cl SnS0 F produced i s a very 3  3  viscous colorless l i q u i d which i s immiscible with the SnCl^.  This  reaction was performed by d i s t i l l i n g an excess of SnCl^ ('v 6 g, 24 mmoles) onto a small amount of S^O^F,, (0.667 g, 3.36 mmoles) i n a 2 o 2 small one part reactor with t e f l o n stem stopcock, and allowing the mixture to warm up gradually to room temperature.  The resulting  mixture was l e f t to react f o r approximately one' hour at room temperature and the excess SnCl^ was then removed by vacuum to y i e l d 2.194  g (6.75 mmoles) of l i q u i d ;  Cl SnS0 F. 3  3  distillation  This compound i s  - 100 -  only moderately stable and decomposes on standing at room temperature for a period of several days. and C^SnCSO^F^.  The decomposition products are SnCl^  Chlorine and t i n analyses were carried out using the  SnS2 method described previously i n the section on C^SnCSO^F) » 2  4.  Br Sn(S0 F) 2  3  2  Dibromotin b i s f l u o r o s u l f a t e was prepared i n a ligand r e d i s t r i b u t i o n reaction s i m i l a r to the one used to make C l S n ( S 0 F ) but because of 2  3  2  the higher melting point of SnBr^ the reaction had to be run either with the a i d of a solvent or i n molten SnBr. at 4 SnBr  4  +  Sn(S0 F) 3  -  4  Typically, an excess of SnBr  4  40°.  2Br Sn(S0 F) 2  3  (2.70 g, 6.16 mmoles) and S n ( S 0 F ) 3  4  (0.263 g, 0.511 mmoles) were ground together to a fine powder i n the dry box and then placed i n a glass tube with a B19 cone and a teflon stem stopcock adaptor top was placed on the tube. contents were heated to 40° (mp of SnBr  4  The reactor and  i s 31°) f o r 24 hours during  which time a cream coloured s o l i d was formed.  The product was  purified  by vacuum subliming the excess SnBr onto a cold finger u n t i l no further 4  sublimation was observed (y 3 days).  Several times during the  sublimation the unsublimed material;;was ground i n the dry box i n order to break up the large lumps of s o l i d . completed white s o l i d B r S n ( S 0 F ) 2  3  2  After the sublimation was  remained.  A l l attempts to synthesize I S n ( S 0 F ) 2  3  i n a similar manner were  2  unsuccessful, iodine was liberated i n a l l cases.  F Sn(S0 F) 2  3  2  has been  142 obtained previously from the reaction of C l S n F 2  2  and S 0 g F 2  2>  - 101 -  C.  Structural Studies The physical properties of SnCSO^F)^, i t s high decomposition  point, i t s i n s o l u b i l i t y i n polar solvents and i t s lack of v o l a t i l i t y suggest that SnCSO^F)^ has a polymeric structure not unlike those of 133 ^ 3^2 ^ °3 ^2 H  S n  S  2A °  F  r  ^ 4  rather than a monomeric structure either 32  nF  tetrahedral l i k e SnCl^ or with chelating SO^F  groups l i k e SnCNO^)^.  This proposal i s confirmed by both the v i b r a t i o n a l spectra which show vibrations due to both terminal and bridging covalent fluorosulfates and the Mossbauer spectra which show a negative isomer s h i f t , small quadrupole s p l i t t i n g and room temperature e f f e c t , as expected for this type of structure. SnF. 4 95,151 Cl Sn(S0 F) 2  3  2  The Mossbauer results are very s i m i l a r to those of  and B r S n ( S 0 F ) 2  3  similar to those of S n ( S 0 F ) 3  4  2  both have physical properties very  and are e a s i l y prepared from S n ( S 0 F )  under mild reaction conditions.  3  4  A s t r u c t u r a l proposal for these  compounds which retains the s i m i l a r i t i e s to S n ( S 0 F ) 3  4  i s one, s i m i l a r  to the structure determined for ( C H ) S n ( S 0 F ) , i n which l i n e a r X-Sn-X 3  groups (X = CI, Br, CHg)  2  3  2  are joined by bidentate bridging SO^F  to form a structure s i m i l a r to SnCSO^F)^ but with the terminal groups replaced by X.  groups SO^F  Both Mossbauer and v i b r a t i o n a l spectra are  consistent with this proposal.  1.  MBssbauer Spectra The Mbssbauer r e s u l t s are shown i n Table 28.  Both 6 and A increase  as the terminal f l u o r o s u l f a t e , (SO^F)^ i s replaced by the progressively less electronegative CI, Br and CH» to form Cl Sn(S0 F) , Br„Sn(S0 F) 9  - 102 Table 28.  Mossbauer Parameters  of )C S n ( S 0 3 p ) 2  6(mm/sec)  Compound Sn(S0jP)4  2  <^>(mn/sec)  H  1.34  0.42  -0.27  Cl Sn(S0 P)  2  0.34  2.29  0.45  Br Su(S0 P)  2  0.58  2.42  0.53  1.82  5.54  0.09  2  5  2  5  (CH ) Sn(S0 F) 3  S n F  2  5  2  -0.26  4  l.dO  151  9 3  0.73  95  Table 29. V i b r a t i o n a l Spectra.  Assignment  Cl Sn(S0 F) 2  IR  3  2  Raman  Br Sn(S0 F) 2  IR  3  2  Raman  Cl^nSC^F IR  Raman  1730 v? vS0 (A")  1385 s  1389 s  1366 s  vS0 (A)  1130 vs  1125 w  1140 s,br  vS0 (A)  1087 s ,br  1089 vs 1061 m  1070 s,br  3  3  3  1350 w  1375 s 1118 s  1085 m  1060 s  1073 w 1004 w  vS-F  864 s  870 s  842 s  865 m  845 s  815 m  6S0  628 m  632 s  613 s  624 s 609  618 m  650 w  5S6 s  587 ms  578 s  584 m  587 m  555 s  552 m  548 s  553 w  554 m  564 w  446 s 420 w, sh  442 s 424 m  406 m  423 w  420 m  423 m  400 m  407 w 383 si  6 S  3  °3  <sso so 3  P  3  v Sn-Cl a v Sn-Cl s pS0 F 3  v Sn-Br s  411 s  312 s  356 vs  369 v:  312 s  316 V7 222 m 165 w  132 w  - 103 -  and (CH^^SnCSO^F^ respectively.  These trends are expected because  as the electronegative (S0.jF) i s replaced by less electronegative t  groups the s electron density at t i n would be expected to increase causing the isomer s h i f t to be larger.  The electronegativity difference  between X and the bridging SO^F groups would also increase causing larger e l e c t r i c f i e l d gradients and hence larger quadrupole s p l i t t i n g s . A room temperature effect i s observed f o r a l l these compounds as expected f o r polymeric structures. The Mossbauer spectrum of Cl^SnSO^F at l i q u i d nitrogen temperature, which was more complicated than any of the other Mossbauer spectra were, consisted of an unsymmetrical three l i n e pattern. suggests that there i s more than one t i n environment the s o l i d state. and +1.62  This result  i n Cl^SnSO^F i n  The three absorption maxima occur at -0.36, +0.85  mm/sec from Sn02> and could be due to one of several possible  combinations of s i n g l e t and quadrupole s p l i t absorptions.  2.  V i b r a t i o n a l spectra SnCSO^F)^ has approximately twice as many peaks i n the region of  the infrared and Raman spectra i n which SO^F modes are expected as Cl Sn(S0 F) 2  for a G  3  2  or B r S n ( S 0 F ) 2  3  2  does.  For C l S n ( S 0 F ) 2  3  the nine modes  2  symmetry fluorosulfate are observed i n the infrared at 1385 cm  g  (vSO), 1130 cm"  1  (v  S0„), 1087 cm"  1  a  2  (v S0„), 864 cm" s 2  1  (vS-F), and  bending and deformation modes at 628, 586, 555, 446, and 312 cm Br Sn(S0 F) 2  3  2  1  1  .  has similar absorptions at 1366, 1140, 1070, 842, and  613, 578, 548, and 406 cm  The positions of these bands are consistent  with those found for other compounds with bidentate fluorosulfates such  - 104 -  as ( C H ) S n ( S 0 F ) . 3  2  3  Sn(S0 F)  2  3  4  shows peaks due to bidentate S0 F at 3  etc. as w e l l as peaks at 1438 (v SO ),  1411, 1130, 1085, 850 cm" , 1  \2"b2 (v S0„), 920 (vSO), and 832 cm"  (vS-F) due to monodentate S0„F.  1  S  2  5  This i s the expected pattern f o r monodentate fluorosulfates. fluorosulfates have v  S0„ i n the 1480-1500 cm range and v S0 a 2 s i and BrS0 F which also has monodentate S0 F has  at 1230-1250 cm" , 1  v  1  o  3  S0„ at 1438 cm" , 2  v  1  a  Gaseous  3  S0„ at 1206 cm" 2  and vSO at 884  1  s  cm" , 1  In the tin-halogen stretching region, C l S n ( S 0 F ) has an IR 2  active v i b r a t i o n at 411 cm  3  2  and a Raman active one at 356 cm .  1  The  1  mutual exclusion rule applies f o r these two peaks indicating l i n e a r i t y for the Cl-Sn-Cl group. spectra of S n ( S 0 F ) 3  4  Neither of these peaks i s observed i n the  and their positions are close to the positions of  the Sn-Cl stretching modes i n SnCl^ which are at 403 cm The symmetric Sn-Br stretch i n B r S n ( S 0 F ) 2  3  1  i s found at 222 cm  2  the Raman spectrum i n good agreement with v SnBr  and 368 cm .  1  Sn-Br at 220 cm  1  1  in  in  s  1 5 2  4 The infrared spectrum of C l S n S 0 F shows that this compound also 3  3  has bridging S0 F groups and eight of the  nine modes expected for  3  C  symmetry S0„F are observed i n the IR spectrum. S  Unfortunately good  .5  Raman spectra could not be obtained and only a few of these bands could be seen i n the Raman spectrum of Cl SnS0 F. The three S0 3  3  modes are observed at 1380, 1118 and 1060 cm \ those found f o r Cl Sn(S0 F> , 2  3  2  (CH ) Sn(S0 F) 3  2  3  2  3  stretching  i n good agreement with  and other bidentate  fluorosulfates. The Sn-Cl stretching frequencies f o r Cl SnS0 F show the absence 3  3  of v g Sn-Cl i n the IR spectrum expected for a trigonal planar S n C l  3  105 group.  In the IR spectrum where v  Sn-Cl would be expected two strong  cl  overlapped peaks are observed, one at 420 cm 400 cm  1  and the second at  No other absorptions are observed down to 300 cm  the transparency l i m i t of the AgBr windows. a medium i n t e n s i t y peak at 423 c i \ strong peak at 369 cm at 316 cm" . 1  1  The Raman spectrum has  a weak peak at 407 cm \  with a shoulder at 383 cm  The peak at 420 1 cm"  1  Sn-Cl and the 369 cm  1  a very  and a weak absorption  1  (IR) and 423 cm  assigned to the SO^ rocking mode, the 400 cm peak to v  which i s  1  1  (Raman) i s  (IR) and 407 cm  1  peak i n the Raman only to v  1  (Raman) Sn-Cl.  S  ct  The Raman absorption at 316 cm  D.  Reactions of Sn(S0^F)^  1.  Introduction  1  would l i k e l y be the ninth SO^F mode.  During the course of this work on Sn(S0 F) . 3  reactions were investigated.  several types of  4  These included r e d i s t r i b u t i o n reactions  with t i n tetrahalides as well as with some other metal tetrachlorides, and complexation reactions both adduct formation and addition reactions with other fluorosulfates and with chlorides and f l u o r i d e s . r e d i s t r i b u t i o n reactions of Sn(S0 F) 3  The ligand  with SnCl^ and SnBr^ have already  4  been discussed i n this chapter and the complexation reactions with C10 S0 F, BrS0 F and I ( S 0 F ) 2  3  3  3  3  are discussed i n Chapter VI.  i n Chapter I I I , the reaction of Sn(S0 F) 3  4  with an excess of (CH^^Sn  was found to y i e l d (CH.^SnSO^F according to  3(CH ) Sn 3  4  +  Sn(S0 F) 3  4  As mentioned  4(CH ) SnS0 F 3  3  3  - 106 -  However, considering the ease with which (CH^)^SnSO^F i s formed i n the s o l v o l y s i s reaction and the length of time required to synthesize SnCSO^F)^, this route cannot be considered an a t t r a c t i v e alternative.  2.  Ligand r e d i s t r i b u t i o n reactions Since Sn(S0 F> 3  4  reacted so readily with SnCl^ to y i e l d  Cl Sn(S0 F)  i n a ligand r e d i s t r i b u t i o n reaction i t was hoped that S n ( S 0 F ) 3  2  3  4  might  react with other group IV tetrahalides to form halofluorosulfato compounds or possibly even polymers containing both t i n and the other group IV element i n alternation joined together i n one molecule by fluorosulfate bridges.  (a)  GeCl  4  andJ3iCl  4  In the case of germanium an excess of GeCl was reacted with 4  approximately 0.3 g of S n ( S 0 F ) 3  4  i n a two part reactor.  The mixture  was s t i r r e d for about one half hour at room temperature without any evidence of reaction except that the vapor pressure i n the reactor increased from  50 mm Hg f o r G e C l  4  alone to 61 mm Hg.  were shown by their infrared spectrum to be G e C l  4  These gases  and S i F  v o l a t i l e s were removed the weight of the flask plus S n ( S 0 F ) 3  v i r t u a l l y unchanged, i . e . no reaction had occurred. Sn(S0 F) 3  4  with S i C l  4  When the  4 >  4  was  The reaction of  attempted under s i m i l a r experimental conditions  was also unsuccessful.  - 107 (b)  TiCl  4  When a large excess of T i C l ^ was added to 0.869 g (1.69 mmoles) of Sn(S0,jF) i n a two part reactor and s t i r r e d for approximately 4  one half hour a largely increased volume of a yellow s o l i d was formed. When the excess T i C l ^ was removed a weight increase to 1.347 g was noted.  This weight corresponds to an uptake of four moles of T i C l ^  per mole of Sn(S0 F) . 3  4  Some of the T i C l ^ could be removed by  extended pumping while slowly r a i s i n g the temperature  to 60° but no  d e f i n i t e product of lower T i C l ^ composition comparable to those found i n the SnCl ~Sn(S0 F) 4  system could be obtained.  3  The yellow s o l i d  was unusual i n that i t was completely devoid of t i n .  Chloride analysis  indicated that the stoichiometry was Cl^gTi^SO^F),^ and microanalytical results for T i , S and F confirmed this r e s u l t .  These analyses are  calculated, T i , 20.60; S, 9.21; CI, 50.90; and F, 5.46; and found, T i , 20.86; S, 9.48; CI, 50.71; and F, 5.51. Although we were f i r s t i n c l i n e d to regard the product as a rather unusual anomaly, subsequent routes to products of i d e n t i c a l properties 153 and composition were found.  TiCl  4  These routes are  (large excess) +  C l ^ T i ^ S O ^ + Cl  T i C l ^ (large excess) + HS0 F 3  and  Cl Ti(S0 F) 2  3  2  +  2TiCl  4  Cl  1 ( )  Ti (S0 F) 3  3  Cl^Ti^SO^  2  2  + 2HC1  - 108 Another unusual feature of this compound i s that there are no peaks i n the IR or Raman spectra, Table 30, i n the region i n which the S-F stretching frequency i s expected. absorption at ^ 660 cm  1  However, there i s a strong  which can only be due to the S-F stretch of  a f l u o r i n e atom which i s involved i n further bidentate bonding.  In  order to achieve six-coordination for a l l three titanium atoms i n this molecule, both SO^F  groups would have to be tetradentate, i . e .  coordinating through a l l three oxygens and the f l u o r i n e , or some of the chlorines would have to be bidentate.  If the tetradenate  SO^F's did  exist i t would explain the unusual p o s i t i o n of the S-F stretch as well as the lack of s i m i l a r i t y between the positions of the SO^ stretching modes i n Cl^jTigCSO  F)  2  and those of other f l u o r o s u l f a t e s .  Supporting  evidence f o r the proposed structure i s found i n HSO^CF^-TiCl^ and HSO^-CH^-TiCl^ systems where tetradentate sulfonate groups cannot occur and under i d e n t i c a l conditions (large excess of T i C l ^ ) the compounds formed that are highest i n chlorine content were Cl^TiSO^CF^ and Cl Ti S0 CH . 3  3  3  1 5 3  3  Addition of donor atoms (adduct or complex formation) should remove the necessity for f l u o r i n e bridging and allow the f l u o r i n e to revert to i t s more normal coordination and vS-F should reappear i n the 800-900 cm"  1  region of the infrared spectrum.  Both N0C1  and P0C1 were  added to C l ^ H ^ S O . ^ ^ i n attempts to check this p o s s i b i l i t y but  3  the  results were inconclusive due to experimental d i f f i c u l t i e s encountered i n i s o l a t i n g the products.  In the NOCl reaction mixtures containing  (N0)„TiGl, were formed. .2 o In order to further investigate this compound attempts were made to prepare titanium fluorosulfates by the more straightforward route of  T  109,  T  TABLE 3 0 V i b r a t i o n a l Spectra o f TiC£ TiC£ CSO.F) 2  CS0 F) 3  IRfcm" ] 1  1248 vs,br  KS0 F  2  Raman[cm ] 1260 ms 1248 m  Raman[cm *] -  | /  1285  1  2  For KS0 F 3  vS0 (E) 3  1205 vw 1188 vw • 1082 m,sh \ 1070 s f  and  Z  J  Assignment  3  -1  (SO„F)  TiCi (S0 F) 2  IR  2 3  3  2  [cm ] -1  1380 m,sh) 1342 s | 1195 m,sh  1082 s  1079  vSOjCAp  1080 ms,sh 1020 s,b  870 vw 650 s ) 643 s,sh /  846 ms  676 ms  755  vSFfA^  732 vs  590 ms  586  6S0 (E)  630 s  579 m  570 ms  570  495 464 430 415  461 m,sh 444 vs  592 m  3  616 m,sh  ms  s vs vs  390 ms  578 m,sh) 555 ms y  •  445 s (448)* 390  407  pS0 FCE) 3  418 sh 390 m* 363 ms*  a) good correspondence between Raman and IR frequencies was noted.  - 110 -  adding S„O^F„ to T i C l . . 2 6 2 4  T i C l . and S 0,F„ reacted i n one part glass 4 262 o  reactors at room temperature or above to produce glassy various compositions presumably  products of  containing fluoro-fluorosulfates or  oxyfluorosulfates of titanium. However, i f an excess of S-O^F^ was added to 0.406 g (2.14 mmoles) 2  D  2  of T i C l ^ i n a one part glass vessel and s t i r r e d at -20° for several hours, 0.720 g (2.27 mmoles) of a yellow s o l i d i d e n t i f i e d by i t s IR 154 spectrum  as C ^ T i t S O ^ F ^ was  TiCl  4  +  S 0 F 2  6  2  produced.  -20° — *  Cl Ti(S0 F) 2  3  2  +  Cl  2  If the excess S 0,.F was removed the s o l i d product was stable at room 2 o 2 o  temperature.  o  This compound can also be produced by the reaction of 154  TiCl  with HS0 F.  4  J H  3  When 9.45  g (29.9 mmoles) of C l T i ( S 0 F ) 2  reacted with a 10 fold excess of T i C l  4  3  was  2  for 20 hours, C l T i ( S 0 F ) 1 Q  3  3  2  was produced i n a ligand r e d i s t r i b u t i o n reaction. Cl Ti(S0 F) 2  3.  3  Complexation  +  2  2TiCl  4  ~  Cl  1 ( )  Ti (S0 F) 3  3  2  reactions  Several attempts were made to prepare complexes i n which the Sn(S0 F)^ acted as an acceptor molecule.  One of these was the  3  preparation of (CIO.) Sn(S0„F) discussed i n Chapter VI. In this 2 2 J o case S n ( S 0 F ) acted as an acceptor of S0 F groups. Attempts were o  3  £  4  3  also made to add both chloride using N0C1 or C1F  3  to form S n ( S 0 F ) C l 3  4  22  and f l u o r i d e using N0 F 2  and S n ( S 0 F ) F 3  4  22  ions respectively.  - I l l-  Although none of these reactions succeeded, some i n t e r e s t i n g side products were formed.  Addition of neutral donors such as POCl^, CH^CN  or (CF^^CO to SnCSO^F)^ to form donors-acceptor adducts were also unsuccessful.  (a)  N0C1  N i t r o s y l chloride, N0C1,  reacts with either SnCSC^F)^ or Cl Sn(S0 F) 2  to produce NOSO_F and (N0) SnCl,. j z o o  3  For the reaction of N0C1 with  C l S n ( S 0 F ) , 0.384 g (0.993 mmoles) of C l S n ( S 0 F ) were added into a 2  3  2  2  3  2  glass reactor i n the dry box and the side arm for addition of s o l i d was sealed o f f . Excess N0C1 was added by vacuum d i s t i l l a t i o n and the reactor was warmed to room temperature.  An immediate vigorous reaction  which produced a yellowish s o l i d occurred and when the excess was removed 0.618  g of the s o l i d remained.  N0C1  This weight corresponds to  an uptake of 3.6 moles of N0C1 per mole of C l S n ( S 0 F ) 2  3  2 >  No v o l a t i l e s  other than N0C1 were observed i n the gas phase and the s o l i d product was shown by i t s infrared spectrum to consist of N0S0„F and (N0) SnCl,. j z o The reaction i s presumably o  4N0C1  +  Cl Sn(S0.F) Z 3 z o  2N0S0 F J  o  o  The reaction of N0C1 with S n ( S 0 F ) 3  4  3  to produce 0.633 g  of S n ( S 0 F ) ) . 3  4  (NO)-SnCl, z o  was carried out i n the same way.  In this case 0.408 g (0.792 mmoles) of S n ( S 0 F ) N0C1  +  4  reacted with excess  of s o l i d (uptake of 4.3 moles of N0C1 per mole  Again only N0C1 was observed i n the gas phase and the  s o l i d was shown to be a mixture of N0S0,F and (N0)„SnCl,.  These two  - 112 components could be separated by subliming the (NO^SnClg.  6N0C1  +  Sn(SO„F). 3 4  »•  4N0S0 F 3 o  +  (NO).SnCl, 2 o  It appears that Sn(SO.jF) undergoes rapid exchange with NOC1  rather  4  than the expected complex formation.  (b)  N0 F and 2  C1F  3  Neither n i t r y l f l u o r i d e , N0 F, or chlorine t r i f l u o r i d e reacted 2  2with S n ( S 0 F ) 3  to produce a complex of the S n ( S 0 F ) F  4  3  reaction with N0 F produced N0 S0 F 2  2  3  4  anion.  2  and that with C1F  The  surprisingly  3  yielded (ClO.).SnF-, even though the reaction was carried out i n a 2 2 o metal reactor.  It must be borne i n mind however that similar experiences 154  when handling chlorine fluorides are not uncommon. Both of these reactions were attempted i n the same manner. Approximately 1 g (2 mmoles) of S n ( S 0 F ) 3  4  was placed i n a metal  reactor i n the dry box, the reactor was then evacuated and an approximately ten f o l d excess of C1F  3  or N0 F was added by d i s t i l l a t i o n . 2  reaction had occurred at room temperature the excess C1F  3  After or N0 F 2  was removed and the i d e n t i t y of the s o l i d products was checked by IR. (c)  Adduct formation  SnF^ interacted with neutral donor molecules such as (CH ) SO to 3  2  form hexa-coordinated donor-acceptor complexes S n F ^ ' 2 D . S n ( S 0 F ) 3  might be expected to form similar complexes so S n ( S 0 F ) 3  4  was mixed  with POCT , CH CN and (CF ) CO i n attempts to form such complexes. 3  3  3  2  When excess P0C1 was d i s t i l l e d onto about one gram of Sn(S0 F) 3  3  4  a  4  - 113 -  greenish-yellow gas ( C ^ ? ) was produced, indicating the f a i l u r e of any intended addition.  Likewise, addition of CH^CN resulted i n the  formation of a viscous yellow o i l after the excess CH^CN was removed i n vacuo from a clear colourless solution of SnCSO^F)^ i n CH^CN. (C7^)^C0, which would be expected to be a rather poor donor, did not interact with Sn(SO„F). when these two components were mixed together.  - 114 -  CHAPTER V CORRELATION OF MOSSBAUER PARAMETERS FOR TIN FLUOROSULFATES  A.  Correlations f o r T i n Fluorosulfates In the preceding chapters the synthesis and s t r u c t u r a l  characterization of a number of tin(IV) and organotin(IV) b i s f l u o r o sulfates of the general type XYSn(S0 F) where X and Y are CH , CI, 3  Br, F, or S0 F has been described. 3  2  3  Vibrational spectroscopy has been  used to i d e n t i f y the bidentate S0 F group and the l i n e a r i t y of the 3  X-Sn-X groups when possible and Mossbauer has been used to establish the presence of hexa-coordination and.the linkage into polymers. Combining information from both techniques has allowed a f a i r l y accurate description of the trans-octahedral geometry around t i n , with confirmation available from the subsequently reported X-ray 135 d i f f r a c t i o n study on ( C H ) S n ( S 0 F ) . 3  2  3  2  Based largely on these data,  a basic description of the bonding i n these and related compounds has emerged. The general contention that a l l XYSn(S0 F) compounds have 24 25 i d e n t i c a l structures, the same as e.g. SnF^ and (CH ) SnF , 3  2  3  2  2  which when s i m p l i f i e d suggests the following environment f o r t i n :  - 115  should r e s u l t i n two predictable parameters 6 and (1)  trends in the p r i n c i p l e Mossbauer  A.  Assuming a constant background i s being provided by  four oxygen (two  from each SO^F  should be a function of the sum ligands X and (2)  -  the  group) the observed isomer s h i f t , of the e l e c t r o n e g a t i v i t i e s of  Y.  The quadrupole s p l i t t i n g , A, w i l l be a function of  the  inductive constant a , the Taft constant, of the ligands X and The p r i n c i p a l conditions (1)  for these two  expected trends are;  changes i n the e l e c t r o n i c environment around t i n are governed  s o l e l y by X and Y, i . e . r e d i s t r i b u t i o n of electron density SO^F  Y.  into  the  groups does not i n t e r f e r e , and (2)  a l l the structures  are reasonably regular, i . e .  contributions  from the asymmetry parameter, n, to A are neglected. Precedents for s i m i l a r correlations abound i n the l i t e r a t u r e .  Some  examples of l i n e a r relationships between <5 and e l e c t r o n e g a t i v i t y  are  22- 22 90 156 hexahalostannate anions SnX, and SnX.Y„ ' ' and the t i n o 4 2 156 * tetrahalides. Examples of l i n e a r relationships between A and a have been found for R^SnBr' s, "^ 1  triphenyltin  haloacetatestrimethyltin  - 116 acetates,  9ft  and R SnX' (R = CH , C H 3  44 and X = F, CI, Br, I ) .  5  A  142 similar trend i s found for the related XYSnF^ series,  a different  slope r e f l e c t i n g the d i f f e r e n t electron dispersing a b i l i t i e s of the F atom and the SO^F  group both i n bridging positions.  As shown i n Figures 18 and 19 such trends are found for both 6" and A for the fluorosulfates and the basic accuracy of the above stated assumptions i s evident. One would suspect that these correlations are not r e s t r i c t e d to the b i s f l u o r o s u l f a t e s but are also applicable to (1) the i s o s t r u c t u r a l 142 oxyacid derivatives or as shown i n part to the f l u o r i d e s ,  to  (2) monofluorosulfates of the type XYZSnS0 F where X, Y and Z are 3  CH , 3  CI, F SO-jF, etc. and of course to (3) other fluorides and oxyacid derivatives.  Two problems are faced here.  F i r s t , for no other oxyacid  derivatives are s u f f i c i e n t l y large numbers of examples known or even obtainable - see the f a i l u r e to extend the use of ligand r e d i s t r i b u t i o n reactions to S0 CF 3  3  derivatives - to allow similar conclusions, and  secondly, monofluorosulfates where one of the ligands i s chlorine need not be s t r i c t l y penta-coordinate because as the c r y s t a l structure 26 of ( C l ^ ^ S n C ^ indicates,  chlorine apparently can act as a weakly  bidentate ligand, capable of d i s t o r t i n g any idealized assumed for such a c o r r e l a t i o n .  geometries  Even a s u p e r f i c i a l inspection of data  obtained on monofluorosulfates indicates a f a i l u r e to r a t i o n a l i z e both <5 and A.  A similar conclusion had been reached previously for some  monofluorides. F i n a l l y the fluorosulfates are exceptional when compared to some reported structures of c a r b o x y l a t e s ' ^ or thiocarbamates ^' 33  3  3  37  (see  Figure \ B  I 3.0  1  1  1  1  4.0  5.0  6.0  7.0  2 of Pauling's  Electronegativities  1 8.0  F i g u r e 13 <X ( C H ) S n ( S 0 F ) 3  2  3  Correlation between laft's inductive constants and the quadrupole Splitting in the series X Sn(SQ F) and X S n F  2  5.0-  2  3  2  ^CH ClSn(S0 F) 3  3  2  2  2  I— I-  1 1  00  I  Br,Sn(SO.F). Cl Sn(S0 F) 2  3  2  b>Sn(S0 F)  2  (S0 F) Sn(S0 F)  2  3  3  1 .O  O  1.0  2.0  3.0  4.0 CT  5.0  6.0  2  7.0  3  8.0  - 119 -  Figure 2).  The carboxylates and thiocarbamates  are anisobidentate,  i . e . , there are differences i n the Sn-0 or Sn-S bond distances, whereas 135 basing our claim on (CH^) Sn(S0 F) 2  3  and the successful correlations  2  for 6 and A, we can regard the SO^F bidenate.  group i n these molecules as i s o -  It i s obvious that anisobidentate groups where the tin-oxygen  (or t i n - s u l f u r ) bond distances depend on the electronic and  steric  properties of other ligands bonded to t i n , do not provide a similar background f o r similar correlations. B.  Other Possible Correlations Two additional correlations may be considered f o r the compounds  discussed i n this study. formula ( C H ) S n ( S 0 A ) 3  2  3  2  For the dimethyltin bissulfonates of general with A = F, C F  3>  CI, CH  3>  C^,  or pj-CgH^CH.^,  the isomer s h i f t , 6, should be a function of the electronegativity of  * A and the quadrupole s p l i t t i n g , A, a function of the Taft constant, a , of A.  Similar correlations had been detected for trimethyltin halo98  acetates,  159 '  (CH ) .jSnCO^CX.^ with X = H, F, Br, or I.  However, for  3  the sulfonates major d i f f i c u l t i e s are encountered.  Group e l e c t r o -  • * ^ , • ,160-162 n e g a t i v i t i e s f o r organic functional groups are often very controversial even when based on thermochemical data, e.g. for the trifluoromethyl group the values reported d i f f e r widely from 2.86  ^®  over 3.10  to  162 3.29,  and are sometimes unavailable as e.g. f o r p-C-H.CH„. ^  4  D  3  Taft constants are available for most systems, however, as a b r i e f *  94  glance at the a  values  of 3.08  and 2.58  for F and CF  3  respectively,  shows the expected differences i n the A values i s not found experimentally for either ( C H ) S n ( S 0 A ) 3  2  3  2  or ( C H ^ S n S O ^ where, as shown i n Tables 16 and  - 120 -  20, 6 and A values for fluorosulfates and trifluoromethanesulfonates are i d e n t i c a l within error l i m i t s .  These experimental findings also  preclude any meaningful isomer s h i f t - e l e c t r o n e g a t i v i t y correlations. It appears safe to say that both 6 and A are very sensitive to changes i n electronegativity or inductive constants of the immediate substituents X and Y, however, long range effects are depicted i n only rough and approximate trends i n <5 and A.  The a b i l i t y of some of the A substituents,  F and CI, to p a r t i c i p a t e i n pir-drr backv donation and the presence of a non-coordinated oxygen, again capable of IT interaction with s u l f u r , may account f o r the discrepancy between sulfonates and haloacetates. No consistent data are available, to relate Mossbauer data of trimethyltin or dimethyltin sulfonates to the d i s s o c i a t i o n constants of the corresponding sulfonic acids.  The determination w i l l require work  i n a non-aqueous solvent, e.g. acetic acid, and from limited data 16 3 available  where values of 4.7 and 6.1 are reported for pKa f o r  HSO^CF^ and HSO^F respectively i t must appear doubtful whether a.meaningf u l c o r r e l a t i o n can be made here. C.  Point Charge Model Correlation of the kind mentioned above involving  quadrupole  s p l i t t i n g values and the Taft inductive constants of some of the substituents on t i n (X and Y) for XYSnCSO^F)^ compounds suggests that these compounds may be suitable model compounds f o r point charge discussions and provide an application of the concept of p a r t i a l quadrupole  splittings  of i n d i v i d u a l substituents. Extension to other sulfonates of the same stoichiometry and even to other geometries such as X»SnS0oF should be  - 121 -  f e a s i b l e provided the coordination polyhedra around t i n are s u f f i c i e n t l y regular.  A large number of geometries have been treated  164 i n this way  f a c i l i t a t i n g the p r e d i c t i o n of the e l e c t r i c f i e l d  gradient tensor with V  the component of prime i n t e r e s t , and the zz p a r t i a l contributions of the i n d i v i d u a l ligands. Different signs f o r V  should be observed  for the two p r i n c i p a l  zz models, the trigonal bipyramidal XYZSnSO^A and the octahedral XYSnCSO^A)^, discussed here and i n Chapter I I I . By comparison to previous work, for the penta-coordinated species V should be positive"^ »165,166 ^ ^ zz 2  a  should be negative for the octahedral compounds.  Some  experimental and computed A's for a number of supposedly  trigonal  bipyramidal compounds are l i s t e d i n Table 31. negative as expected  The computed values are  for trigonal bipyramidal structures but for a l l  methylchlorotin compounds a s a t i s f a c t o r y f i t i s achieved only when strong contributions from the asymmetry parameter are assumed. 166 of a sign reversal cannot be ruled out completely necessary to obtain this information experimentally.  The p o s s i b i l i t y  and i t i s For the cases  l i s t e d above, application of an external magnetic f i e l d at 4°K w i l l 119 remove the degeneracy of the 3/2 excited state of the Sn nucleus. 92 166—168 A number of magnetic perturbation studies have been published  '  and work on a series of compounds, whose synthesis has been discussed i n this thesis, has commenced, but the discussion of these measurements w i l l exceed the scope of this thesis.  -  122  -  Table Point-charge  Predictions  Compound  for  o.(obs)  31 soae  Methyltin(IV)  /L\{pre&)  Compounds  <^(pred)  mm/sec  mm/sec  (CH3)5SnS0^Ci,3  4.57  -4.56  0  (CH5)3&nS05CH5  4.21  -4.12  0  (CH-5)2ClSnS0-jP  4.69  -4.05  0.64  CH-jClgSnSO-jP  3.25  -3-30  0.81  4.06  -4.07  0  3«90  -4.10  0  3.80  -3.58  0.74  2.69  -2.84  0.98  ( C H ^ S n ( C H ^ S n F  2  S04  1 4 2  (CH3)2ClSnP CH3Cl2SnP  1 4 2  1 A 2  1 4 0  mm/sec  - 123 -  CHAPTER VI THE HEXAKISFLUOROSULFATOSTANNATE(IV) ION A.  Introduction Although hexahalogen metallates,  (MX^)  n  , of group I l i a , IVa, and  Va metals are well known, no examples of analogous fluorosulfates have been reported.  For fluorosulfates, the largest number of SO^F groups  bonded to a central atom appears to be four observed i n the anions ~  — 169  BrCSO^F)^  — 163 and iCSO^F)^ ,  i n the neutral compounds such as  62 C(SO.jF)  and SnCSO^F)^ and i n the mixed fluorofluorosulfato anion  4  SbF^CSO^F)^  which was i d e n t i f i e d i n solution only.  Judging from the structure proposed for Sn(S0 F) , i t seems l i k e l y 3  4  that t i n would be a suitable central atom for a M(S0 F) " anion. 3 o 2Two synthetic routes to compounds with the Sn(SO„F) anion were 3 o attempted. These are the i n t e r a c t i o n of SnCSO^F)^ as a fluorosulfate ion acceptor with a suitable fluorosulfate and the complete substitution 2of CI i n the SnCl^ ion by S0 F using S„0,F„ as the fluorosulfonating o J 2 o 2 agent. The f i r s t method was used to make (C10„) Sn(S0„F) o  o  o  2 2.  [Br(S0 F) ] Sn(S0 F) 3  2  2  3  6  and [ I ( S 0 F ) ] S n ( S 0 F > 3  2  2  3  6  J  O  from S n ( S 0 F ) 3  4  and the  second to make K Sn(S0„F)., Cs Sn(S0„F), and (NO) Sn(S0 F), from 2 5 o 2 3 D 2 j o K SnCl., Cs SnCl, and (N0) SnCl, respectively. The structures of 2 o 2 o 2 b o  0  0  o  o  o  o  these compounds were investigated using v i b r a t i o n a l and Mossbauer spectroscopies.  Solution studies i n HSO-jF were of s p e c i a l interest  - 124 -  because the parent acid H Sn(S0„F),. can be expected to be a strong acid, 2 j o 101 perhaps comparable to HSbF (S0 F) one of the main components of , - 170 super acid. o  2  B. 1.  3  4  Preparations (C10 ) Sn(S0 F) 2  2  3  6  The work described i n this chapter was started a f t e r low melting solids were obtained accidentally i n the attempted preparation of SnCSO^F)^ at temperatures above 100° i n the presence of considerable amounts of chlorine or secondary products such as CISO^F and C10 S0 F. 2  3  The observed weight increase was i n excess of the expected weight for the formation of SnCSO^)^. Pure d i c h l o r y l hexakisfluorosulfatostannate(IV) was prepared v i a a complexation reaction of SnCSO^F)^ with CK^SO^F.  2C10 S0 F 2  +  3  Sn(S0 F) 3  >  4  (ClO^SnCSC^  2 6 2 This reaction was carried out i n a 100 ml erlenmeyer f l a s k equipped with a t e f l o n stem stopcock and containing a teflon coated magnetic  stirring  bar by adding 0.849 g (5.02 mmoles) of C10 S0 F onto 0.520 g (1.01 2  mmoles) of S n ( S 0 F ) 3  4  3  i n the dry box at room temperature.  To ensure  good mixing about 10 ml of S.0,F were then added by vacuum d i s t i l l a t i o n . 2 o 2 The reaction mixture was heated to about 70° and s t i r r e d for several o  hours.  0.793 g (0.96 mmoles) of a bright yellow s o l i d , l a t e r i d e n t i f i e d  as (C10.)_Sn(S0„F). were isolated after the S_0,F„ and the excess 2 2 3 o 2 o 2 C10„S0„F were removed by vacuum d i s t i l l a t i o n . 2 J  (CIO.)_Sn(S0„F), i s a 2 2 j o  bright yellow s o l i d thermally stable up to 130° where i t decomposes to  - 125 -  a red l i q u i d .  I t hydrolyses very vigorously to a clear chloride free  solution.  2.  [Br(S0 F) ] Sn(S0 F) 3  2  2  3  6  [Br(S0.F)„] Sn(S0„F) , was prepared i n two stages f i r s t by the J 2 2 3 o o  /  reaction of BrSC^F  with S n ( S 0 F ) 3  to form a red-brown s o l i d  4  containing  2Sn(SO.F),  possibly Br Sn(S0.F), followed by reaction of this compound 2 j o with excess S„0,F„ to produce pale yellow p r e c i p i t a t e of 2 o 2 o  J O  [Br(S0 F) ] Sn(S0 F) . 3  2  2  3  6  2BrS0 F  +  3  Sn(S0 F) 3  Sn(S0 F) -2BrS0 F 3  4  3  Sn(S0 F) '2BrS0 F  4  3  +  2S 0 F 2  6  —-*  2  4  3  [Br (SC^F) ] Sn(S0 F) 2  2  3  In a t y p i c a l reaction, a small excess of BrS0 F (^1 ml) was added by 3  d i s t i l l a t i o n onto 0.354 g (0.688 mmoles) of S n ( S 0 F ) i n a one part 3  4  round bottomed f l a s k reactor with t e f l o n stem stopcock.  These  components were reacted at room temperature for three days to produce 0.601 g (0.689 mmoles) of Sn(S0 F) •2BrS0 F. 3  4  3  After the excess BrS0 F 3  was removed by d i s t i l l a t i o n approximately f i v e grams (25 mmoles) of S  2°6 2 F  W  a  S  a  d  d  e  d  o  n  t  o  t h e  Sn(S0 F) -2BrS0 F by d i s t i l l a t i o n . 3  4  3  A slow  reaction occurred to produce a viscous yellow l i q u i d soluble i n S„0,F„ 2 o 2 from which a pale yellow s o l i d slowly separated out. The [Br(S0„F) ]„Sn(S0 F ) . was isolated on a f r i t when the S_0,F„ solution 3 2 2 3 6 2o2 o  was f i l t e r e d at -40°. the  S 0 F 2  6  2  The product could not be isolated by removing  by d i s t i l l a t i o n because the [ B r ( S 0 F ) ] S n ( S 0 F ) 3  2  2  3  6  in  - 126 decomposed on pumping. yellow  [Br(SO„F)_].Sn(SO.F), melts at 48-50° to a 3 2 2 J O  liquid.  3.  [I(S0 F) ] Sn(S0 F) 3  2  2  3  6  Stoichiometric amounts of I ( S 0 F ) 3  melting point of I ( S 0 F ) 3  slowly c r y s t a l l i z e d  3  and S n ( S 0 F )  3  3  to produce a viscous yellow l i q u i d which  to pale yellow  [I(S0„F)-]„Sn(S0 F),. o  5  2I(S0 F) 3  +  3  react at the  4  Sn(S0 F) 3  3 4  5  2 2  ° ^  J O  [I(S0 F) ] Sn(S0 F> 3  2  2  In this preparation, 1.522 g (1.01 mmoles of S n ( S 0 F ) 3  dry box to 1.72 g (1.03 mmoles) of I ( S 0 F ) 3  3  3  4  6  were added i n the  i n a round bottom f l a s k  with a t e f l o n stopcock adaptor top. These reactants were heated to 35° where a<'. reaction occurred to form a viscous yellow  liquid.  About  10 grams of S^O^F. were added to f a c i l i t a t e the reaction by providing 2 o 2 a diluting hours.  agent and these compounds were s t i r r e d at 35° f o r several  The S 0 1 . was then removed and the viscous yellow 2 o 2  remained.  liquid  This l i q u i d slowly s o l i d i f i e d over a period of about f i v e  days at room temperature to y i e l d 2.35 g (1.06 mmoles) of pale yellow [I(S0 F) ] Sn(S0 F) . 3  4.  2  2  3  6  K Sn(S0 F) , Cs Sn(S0 F) 2  3  6  2  3  6  and (NO) Sn(S0 F) 2  3  6  The potassium,cesium and nitrosonium salts were prepared i n reactors similar to the one used i n the (C10 )-Sn(SO.F), preparation 2 2 3 o by a ligand substitution reaction. o  - 127 -  M^SnClg  M  +  3S 0 F 2  6  2  f^"  -  M Sn(S0 F) I  2  3  6  +  3C1  2  = K, Cs, or NO  1  In the case of Cs Sn(S0„F) , for example, a f i v e - f o l d excess of S 0 F 2 j o 2 o 2 o  o  c  o  ( 10 g) was d i s t i l l e d i n vacuo onto 0.731 g (1.22 mmoles) of c a r e f u l l y dried Cs SnClg.  The mixture was allowed to warm to room temperature  2  where a slow reaction with evolution of chlorine occurred.  The reactor  was then heated to 50° f o r about three hours while s t i r r i n g the mixture magnetically.  When a l l gas evolution had ceased, the excess S 0 F 2 O 2  was removed by vacuum d i s t i l l a t i o n and 1.211  g (1.24 mmoles) of white  s o l i d Cs_Sn(S0„F), were obtained as a nonvolatile residue. 2  2  6  Both  K S n ( S 0 F ) and (NO) Sn(S0 F) were obtained i n the same way, 2 j 6 2 j 6 0  o  £  temperature was 60° f o r the former and 50° f o r the l a t t e r .  the reaction  A l l three  of these compounds are hygroscopic white s o l i d s . A l l of the Sn(S0„F) j o  2-  compounds, i n p a r t i c u l a r the K and Cs  £  s a l t s , show reasonably high thermal s t a b i l i t y .  This suggests that the  preparation of other s a l t s , e.g. Rb Sn(S0„F), or Na Sn(S0 F). may 2 j 6 2 J 6 o  o  f e a s i b l e , but no attempts at their synthesis were made.  o  be  A l l of these  compounds are soluble i n HSO^F quite i n contrast to Sn(S0 F) . 3  4  This  contrast serves as preliminary evidence that the products are.not merely mixtures of Sn(S0,jF) and MSO^F. 4  The melting points and  a n a l y t i c a l results f o r the s i x compounds are l i s t e d i n Table 32. Another possible route to compounds of this type, the heterocation substitution of C 1 0  + 2  by N0  +  or N 0  + 2  was attempted i n the reaction of  (C10„) Sn(S0„F), with an excess of NO or N0„ at room temperature. 2 2 j o 2 o  The  - 128 Table 32.  A n a l y t i c a l Results.  Compound  lis ( ^e») Analysis  mp  1  Calculated K_Sn(S0 F) 2  o  235-8  /:  3 D  Cs Sn(S0 F), 2 J o o  249-53  o  (N0) Sn(S0 F), 2 o  o  3 D  (C10-) Sn(S0_F), o  2. 2.  94-7  130  Found  Sn  15.00  14.84  S  24.31  24.58  F  14.41  14.20  Sn  12.13  11.80  S  19.65  19.60  F  11.65  11.54  Sn  15.35  15.57  S  24.88  25.00  F  14.75  15.02  Sn  14.00  14.25  S  22.69  22.84  F  13.44  13.65  8.36  8.11  3 D  CI  - 129 expected formation of CINO^, ''"' 17  172  i d e n t i f i e d by i t s IR spectrum,"  73  took place, but the s o l i d residue always contained small amounts of indicating incomplete reaction as well as some i o n i c SO^F  due to  the formation of NOSC^F or NC^SC^F.  C.  Mossbauer Spectra 119 The  Sn Mossbauer data recorded for the hexakisfluorosulfato-  stannates are l i s t e d i n Table 33 together with for a number of related compounds.  l i t e r a t u r e values  A l l the hexakisfluorosulfato-  stannates except Sn(S0 F) «2BrS0 F gave single l i n e spectra with very 3  4  3  similar isomer s h i f t values, however, the wider l i n e widths the NO,  CK^,  BrCSOgF^ and ICSO^F^ compounds may  (r)  for  indicate some  unresolved s p l i t t i n g s i n these spectra and hence distorted octahedral structures for these compounds.  SnCSO^F^^BrSO^F i s the only compound  whose MBssbauer spectrum d i f f e r s s i g n i f i c a n t l y from the rest.  I t has  both a higher isomer s h i f t and a small but resolved quadrupole  splitting.  These two differences suggest that the two SO^F  groups are not t o t a l l y  abstracted from BrSO^F by SnCSO^F)^ and the resulting complex may resemble an adduct with the previously uncoordinated oxygens of BrSO^F + 174 coordinating to SnCSO^F)^. A Br cation would be unlikely and no evidence for i t has been found. 137 In general, the s i m i l a r i t y of the fluoro .whose  Mossbauer' data  are  and fluorosulfato compounds  recorded here i s apparent, p a r t i c u l a r l y 95  the t r a n s i t i o n from well resolved quadrupole  s p l i t t i n g s for SnF^  SnCSO^F)^ to single l i n e spectra for the anionic complexes.  However,  some interesting differences between the fluoro and fluorosulfato compounds deserve attention.  and  - 130 Table 33.  Mossbauer Spectra at 80°K.  Compound  6 (mm/sec)  A (mm/sec)  Line Width  R  CO K Sn(S0 F) 2  3  6  Cs Sn(S0 F) 2  3  6  (NO) Sn(S0 F) 2  3  6  (C10 ) Sn(S0 F) 2  2  3  6  Sn(S0 F) -2BrS0 F 3  4  3  [Br(S0 F) ] Sn(S0 F) 3  2  2  3  [I(S0 F) ] Sn(S0 F) 3  2  Sn(S0 F) 3  2  3  4  SnF. 4  0  1.14  -0.25  0  1.11  -0.28  0  1.41  -0.30  0  1.28  -0.16  0.87  -0.23  0  1.29  -0.25  0  1.45  -0.27  1.34  -0.26  K SnF 2  1 3 7 6  (C10 ) SnF 2  2  K SnCl, 2 6 0  6  6  -0.26  1 6  3  7  Li 29,1.26  1.05,1.32 95  151  0  -0.40  1.01  +0.48  0  0.42 0.73  1.80  -0.43  0  95 i  1.59  0.61  1.46,1.46  0.71  1.35  0.38  - 131 -  Although SnF^ ^""^ and SnCSO^F)^ have i d e n t i c a l isomer s h i f t s , the isomer s h i f t s of the hexafluorostannates are about 0.10 to 0.15 mm/sec lower than those of the hexakisfluorosulfatostannates.  This  difference indicates a s l i g h t l y higher e f f e c t i v e nuclear charge on t i n for the l a t t e r group of compounds, probably caused by a lower electronegativity of the fluorosulfate group.  In l i g h t of recent  i. . 22,156,175,176 ^ . ,. , . discussions, i t does not seem meaningful to derive electronegativity values for the SO^F group from the.sedata. The absence of any observable quadrupole s p l i t t i n g s for (C10 )„Sn(S0„F),. contrasts with the observation for (C10„)„SnF, where 2 2 j o 2 2 b 137 o  a s p l i t t i n g of 1.01 mm/sec was observed.  Since i n ( C K ^ ^ S n F ^ the  s p l i t t i n g i s caused by appreciable anion-cation interaction i t must be concluded that a similar i n t e r a c t i o n i s either absent i n (C10_)_Sn(S0„F) 2  2  J  or i t s e f f e c t i s e f f e c t i v e l y buffered by the larger SO^F groups and not relayed to the t i n atom to the same extent that i t i s i n the hexafluorostannate ion. F i n a l l y , whereas a l l hexafluorostannates give well resolved spectra at room temperature, the f l u o r o s u l f a t e derivatives do not seem to show the same behaviour.  No resolvable spectrum could be obtained at room  temperature for K S n ( S 0 F ) . (C10 > Sn(S0 F) , [ B r ( S 0 F ) ^ S n ( S 0 F ) and [I(S0„F) ] Sn(S0„F) were found to interact with the mylar windows 2  3  o  o  2 2  at room temperature.  3  6  2  2  3  6  3  2  3  6  £  J O  With the bromine and iodine derivatives the  reaction with the mylar occurred so rapidly that teflon windows had to be used instead of the mylar ones.  o  - 132 -  D.  V i b r a t i o n a l Spectra Both Raman and infrared spectra (only down to ^ 300 cm  only s i l v e r halide  windows were found to be inert to attack) were  recorded for K S n ( S 0 F ) , Cs Sn(S0 F) 2  because  1  3  6  2  3  , (N0) Sn(S0 F) 2  3  6>  and ( C 1 0 ) S n ( S 0 F ) 2  2  3  6  and Raman spectra only for [Br(S0„F)_] Sn(S0„F). and [I(S0„F)„]„Sn(S0„F). j 2 2 J O j 2 z J O o  because these compounds reacted with even AgCl windows.  No reasonable  spectra of the dark brown Sn(S0 F) .2BrS0 F could be recorded because 3  4  3  of window attack i n the case of IR spectra and lack of transparency i n the case of the Raman spectra.  The spectral results are l i s t e d i n  Tables 34, 35 and 36. 2As expected, absorption bands due to the Sn(S0 F) j o i n the same regions f o r a l l ^six  compounds.  ion are found  Although reasonably good  general agreement with previous work on monodentate S0 F groups i s 3  noted, extensive v i b r a t i o n a l coupling and s o l i d state s p l i t t i n g results i n complex absorption bands, p a r t i c u l a r l y i n the S-0 and S-F stretching regions.  These e f f e c t s are more apparent i n the Raman spectra than  i n the poorly resolved infrared spectra. The spectra of [Br(S0 F) ] Sn(.S0 F)^ and [I(S0,F)_]„Sn(S0_F), and to a lesser extent (C10 ) Sn(S0 F). are 3 2 2 j o 2 2 j o further complicated by the large number of vibrations due to the 3  o  o  2  2  o  2cations most of which are found i n the same region as the Sn(S0„F) j o vibrations are. Since for [Br(S0„F)„] Sn(S0„F), or [I(S0„F) ] Sn(S0„F), j 2 2 J O J 2 2 J O o  o  o  the S0 F groups attached to both Br (or I) and Sn are expected to be 3  monodentate extensive overlap i s expected and a d i f f e r e n t i a t i o n between the two w i l l be impossible. Because of the lack of cation vibrations and the unlikeliness of cation-anion interactions, the spectra of K„Sn(S0.F) z J O  and Cs Sn(S0„F) z j o o  3  - 133 -  Table 34. Vibrational Spectra of A l k a l i Metal  Hexakis(fluorosulfato)-  stannates(IV).  K Sn(S0 F) 2  IR  1360 br 1200 br,s  3  Cs Sn(S0 F)  6  2  Raman  1407 1390 1278 1228  m m s w  1096 s 990 br,s 800 br ,s  1002 859 836 823  m m m m  IR  3  6  Raman  1375 s,br 1260 sh 1205 s,br  1407 } m 1399 1270 s 1218 w  1080 sh  1091 s  990 s,br  995 m  800 s,br  828 m 811 m  Assignment  } v S0 a 2  9  ?  V°2 } v SO } v SF  620 s  625 s  621 m  625 s  SnOS0 bend  571 sh  582 m  570 sh  578 s  S0  2  bend  550 s  560 w  550 s  560 s  S0  2  rock  430 m  432 m 416 w  2  431 m 422 w,sh  418 } w 407  SF wag SO wag  360 sh 346 mw  345 w  vSn-0  266 mw  260 mw  S0 F torsion o  - 134 Table 35. V i b r a t i o n a l Spectra of Heterocation  Hexakis(fluorosulfato)-  stannates(IV).  (C10 ) Sn(S0 F) 2  IR  2  3  (NO) Sn(S0 F) 2  6  Raman  1420 m,sh  1412 w  1378  1386 s  1303 w 1290 m  1308 w 1295 w 1206 s  Raman  2305 w  2334 m 1398 m  1360 br  Assignment VN0 V  +  a °2 S  1385 m v C10 3  1200 s,br  + 2  1  1272 s 1221 m V  1092 m 1025  6  IR  1265 ms 1215 s,br 1180 m, sh  3  s °2 S  ?  1096 vs  1062 s  V 2 10  1008 995 m, sh  990 sh  830 s,br , 810s, sh  842 m 820 m  1000 s,br  1026 w 1010 w  +  vSO  800 s ,br  842 m 822 sh 814 m  vSF  628 m  624 s  620 m 600 sh  623 s 604 m  SnOSO. bend z  576 m  582 m  575 s  585 m  S0 bend  550 m  555 m  555 s  559 s  S0  519 m  526 m  430 m  429 m  420 sh 428 sh  435 w  SF wag  402 m  399 w  -  - 408 w  SO wag  2  rock  v C10 2  348 m 264 w  2  355 347 262 w  w  + 2  vSn-0 S0 F torsion 2  - 135 -  Table 36.  V i b r a t i o n a l Spectra of Halogen B i s f l u o r o s u l f a t o  Hexkis-  fluorosulfato Stannate(IV).  ,[Br(SO-F) ] Sn(S0 F) 2  2  Raman  3  6  [I(S0 F) J Sn(S0 F) 3  2  2  3  Assignment  6  Raman  1497 w  v S0„ cation a 2  1420 vw 1387 m  1384 w 1370 w  1248 s 1197 m  1251 s 1213 m 1184 m  1145 1092 1020 985 865 830 745  m m w w vs w vs  v S0„ cation s 2 }  V S0 s  2  ? 1106 1010 963 882 826  m w s m w  663 vs 652 vs  } v SO. a 2  652 s  vSO vSO cation vSF cation vSF v Br-0 a v 1-0 a SnOS0 bend v Br-0 s v 1-0 s 2  640 s 631 m 596 w 558 w  580 m  S0  2  bend  562 m  S0  2  rock  530 w 464 vs 430 414 386 367  vw m w w  6BrOS bend 456 435 412 384 370 331  w w w vw w m  309 vs 264 w  287 w 254 w 163 w,sh  SF wag SO wag vSn-0 6I0S bend SBrOS wag <SI0S wag S0 F torsion 2  -  9CT  -  - 137 -  should be the simplest.  The general features of these spectra  are  2repeated  i n a l l the other Sn(SO_F), 3 o  derivatives and serve as a good  s t a r t i n g point for discussions of the v i b r a t i o n a l spectra. SO^  The  three  stretching modes and the S-F stretch are found at ^1400, ^1200,  ^ 1000,  and ^830  cm  and are i n the regions expected for SO^ and  1  vibrations of monodentate SO^F  compounds.  The s p l i t t i n g ,  S-F  of these  bands i s not unexpected, however i t seems rather unreasonable to account for the bands at the 1200  or 1000  below 700 cm  1  1270 cm  and 1090 systems.  1  cm  i n the Raman spectra as part of  1  The remaining bands at frequencies  can be tentatively assigned as shown i n Table 34.  The  absence of any vS-F c h a r a c t e r i s t i c of i o n i c fluorosulfates i n the 750-800 cm  region i s good additional evidence for the existence of 2discrete Sn(S0„F) ions rather than formulation as mixtures of 3 o 1  £  SnCSO^F)^ and KSO^F or CsSO^F respectively and complements the Mossbauer results n i c e l y . Tne (C10_)-Sn(SO_F). and  (NO)_Sn(S0„F). spectra, Table 35, have 2 3 o 2absorption bands due to the Sn(SO.F). corresponding to those of the 3 o 2 2  J O  potassium or cesium compounds as well as bands due to the heterocations. No a d d i t i o n a l s p l i t t i n g of the SO^F vibrations,  at 1060  at 526 cm  The C102  +  at 1308 and 1295 cm + 137 177 are i n agreement with previous observations on ClO^ ' is 35 37 s p l i t into two components presumably due to CI and CI isotopes as observed previously.  cm \  bands i s observed. 1  and  In (NO) Sn(S0.F),, vN-0 o  2  i s found at 2334  1  cm"  1  j o  137 i n (N0) SnF^ rather than the value I 6 —1 137 178 of 2207 cm reported for (NO)-SnCl-. ' These findings for the and compares well with 2325 cm  -1  o  2  O  heterocation complexes are thus consistent with ionic formulations CK>  + 2  and N0  +  cations.  with  - 138 -  The Raman spectra of [ B r ( S 0 F ) ] S n ( S 0 F ) 3  2  2  3  and  6  [I(S0 F) ] Sn(S0 F) 3  2  2  3  6 >  Table 36, are considerably more complex than those of the previous four compounds, however, a l l but two of the absorption bands seen i n K Sn(S0„F)^ are found here i n very similar positions. 2 j o  The  o  band at 1278 cm and the 625 cm  i n K„Sn(SO-F), i s missing i n both of these complexes 2 3 o  1  1  unassigned  band tentatively assigned to an S0  shifted by 25 cm"  1  to 652 cm  -1  3  bending mode i s  i n both [ B r ( S 0 F ) ] S n ( S 0 F ) 3  2  2  3  and  6  [I(S0 F) ] Sn(S0 F) . 3  2  2  3  6  There are ten additional bands which could be due to the B r ( S 0 F ) 3  + 2  cation i n the Raman spectrum of [Br(SO„F)„]_Sn(SO_F),. These bands can 3 2 2 j o be assigned with the help of some l i t e r a t u r e data and the Raman spectrum of Br(SO.F)„SbF (discussed more f u l l y i n Chapter VII). G i l l e s p i e and 3 2 6 179 + Morton i d e n t i f i e d the Br(SC> F) cation i n the HS0 F/SbF -solvent 3  2  3  5  system and recorded a Raman spectrum of this solution and attributed three bands to the cation, however, since these bands are also found i n B r ( S F ) , the assignment to the B r ( S 0 F ) n  3  3  as questionable.  3  ion must be regarded  + 2  These values as w e l l as the Br(SC> F) 3  + 2  modes of  Br(S0 F) SbF. and the ten bands i n [Br(SO„F).] Sn(S0„F), are l i s t e d 3 2 o j 2 2 j o o  o  o  i n Table 37. Looking f i r s t at the S  n 3  stretching modes, they are i n f a i r l y  t y p i c a l positions f o r monodentate S0 F although the 1500 cm  band  1  3  seems to be at f a i r l y high energy for a s o l i d compound. 1424 cm"  1  i n "KBr(Sd F).^  1 6 9  and 1490 cm"  1  i s probably reasonable f o r B r ( S 0 F ) . +  3  2  in Br(S0 F) , 3  3  vS-0 i s at 1 6 9  so 1497  Only one of these S0  3  cm"  1  stretching  179 modes was observed i n the super acid solution.,  but since the observed  - 139 -  Table 37.  Br(S0 F)  Br(S0 F) SbF 3  2  3  6  2  Vibrational Modes.  Br(S0 F) 3  [Br(S0 F) ] Sn(S0 F) 3  2  2  1497  "1514 1254  2  1242  1248  3  6  Assignment  v SO. a 2  V°2  980  985  vSO  875  865  vS-F  720  745  v Br-0 a  616  640  v Br-0 s  468  462  464  SOBr bend  320  308  309  SOBr wag  - 140  peak i s by f a r the most intense of the three i n [Br(SO.F).]_Sn(S0 F), or 3 z Z J o Br(S0„F)„SbF^, this result seems reasonable. The S-F stretch i s j z o o  assigned to the band at 865 cm  1  i n the t i n compound.  The remaining bands cannot be assigned with certainty.  The  d i f f i c u l t i e s a r i s e because of the lack of data on Br-0 stretching frequencies and the general uncertainty i n the region below 600 cm  1  due to overlap of modes due to the cation with those of the anion. Literature values on bromine-oxygen stretching modes are available for the f l u o r o s u l f ates BrSO^F ^ and BrCSO^F)^  and the anions  7<  Br(S0 F) " 3  7  and B r ( S 0 F ) ~ .  0  2  3  In addition values f o r Br 0  1 6 9  4  1  8  0  2  181 (with bridging oxygen) and Br0 F  - 182 and Br0  3  are reported and the  3  assigned stretching modes f o r a l l these compounds are l i s t e d i n Table 38.  In [Br(S0-F) ]„Sn(S0.F), the only possible assignment f o r Br-0 3 z z j o o  stretching modes are two bands at 745 and 640 cm ^.  This region i s  free from S0 F vibrations (stretching modes are higher than 800 cm  1  3  and bending modes should be below 630 cm "*). would be expected for a bent B r 0  2  Two stretching modes  grouping.  Although i t i s reasonable to expect an increase i n Br-0 stretching frequencies when going from the anion B r ( S 0 F ) 3  molecule B r ( S 0 F ) 3  3  4  over the neutral  to a cation as shown by the corresponding trends  for Br-F derivatives, i t appears that previous assignments for Br-0 stretching modes i n the S0 F derivatives are decidedly too low and 3  should be reassigned. Br(S0 F)  For instance, i n the case of BrS0 F and the 3  assignment more consistent with the subsequently 69 published spectra of the halogen fluorosulfates FS0 F and C1S0 F 3  2  ion an  3  3  -  141  -  Table Literature Compound  V  Values  38 f o r S>Br-0  and  i)Br-F  \) B r - F ( c m " 1 )  Br-OCcm"1) 464  BrS03F  Br(S03* )  455,  ,  3  Ref.  70 384  169 70  Br(S03F)2~  437  Br(S03F)4~  447,  Br 0  587  BrOjF  974,  875  181  Br03"  836,  806  182  2  169  399  180  457  532,  184  BrF2~  596  BrF  3  674,  613,  BrF  2  715,  706  +  Table Br-0  Stretches  Compound  39  in Fluorosulfates \)  Br(S0 F)  4  615  Br(S0 F)  2  618  3  3  BrSOjF  Br-0  659  Br(S0 F)  3  721, 6 4 5 ,  Br(S0 F)  2  745,  3  3  640  183  612  581  185 183  - 142 -  would place vBr-0 for BrSO^F at 659 cm  1  and the Raman active BrO^  stetch f o r a presumably l i n e a r O-Br-0 configuration i n BrCSO^F^ 618 cm ^.  at  In a very similar way assignments f o r the t r i v a l e n t deriva-  tives Br(SO„F)  and Br(SO F)  at 721, 645 and 612 cm  1  w i l l have to be revised.  Strong bands  are more appropropriately assigned to the  expected three Br-0 stretching modes i n BrCSO^F)^ and f o r the anion a strong band at 615 cm  1  i s at least one of the Br-0 stretches. The  remaining frequencies can again be accounted f o r assuming monodentate SO^F  groups but a concrete r e v i s i o n appears to be beyond the scope  of this thesis.  The new assignments are shown i n Table 39 to indicate  the trends i n vBr-O. The positions of the Br-0 stretching modes i n BrCSO^F)^"^ should also be confirmed by positions of corresponding modes f o r the I(S0.jF)2 cation and indeed bands at 663 and 631 cm  1  +  are most conveniently assigned  as the asymmetric and symmetric stretches i n [iCSO.jF^^Sn^O.jF)^.  E.  Solution Studies i n HSO^F  The solutions of K„Sn(S0 F). and (C10„).Sn(SO„F). i n HSO-F are 2 3 o 2 2 3 o J both i o n i c , but the solutes are less f u l l y dissociated than KSO^F i s . o  These solutions were shown to be basic by t i t r a t i o n of a solution of K Sn(S0„F),, i n HSO.F with the standard base KSO_F. 2 j o 3 3 _2 o  calculated f o r concentrations up to 6 x 10 Table 40.  They  values  moles/kg are l i s t e d i n  A plot of concentration vs. s p e c i f i c conductance i s shown  i n Figure 21. As shown i n the figure, the solutions of (CIO.)„Sn(S0.F) are 2 2 3 b s l i g h t l y less conducting than those of K_Sn(S0„F) . The same order has 2 3 o been observed previously f o r solutions of KSO^F and CK^SO^F i n HSO^F ^ ® £  £  - 143 -  TABLE E l e c t r i c a l Conductance of K„ [SnCS0 F),J and l J O o  CCA0 ) [SnCS0 F) J i n HSC^F at 25.00°C; 2  2  3  6  Y Values  K^SnCSCy)^  Y values f o r , v CC£0 ) lSnCS0 F) J  10  0.73  0.59  15  0.63  0.55  20  0.58  0.51  25  0.55  0.48  30  0.52  0.45  35  0.49  0.44  S p e c i f i c Conductance [ohm-1 cm ] x 10 -1  a)  4  y values f o r  b;  2  2  3  -4 _, concentration range: 1.6 to 6.3 x 10~ x 10 experimental  2  moles kg ^^experimental concentration range: 3.0 x 10" to 3.5 x 10~ 5  moles kg  2  6  <r 144 -  Figure 21.  Conductivities of K [Sn(S0 F) 2  3  (  and  (Cl0 ) [Sn(S0 F) ] at 25 °C 2 2  10  20  3  30  6  40  50  60  C [moles kg-]x 10  3  - 145  -  and has been attributed to differences i n the m o b i l i t i e s of the solvated cations.  The formation of the solvated C l O ^  indicated by the yellow-red  cation i s  color of the solutions of K^SnCSO^F)^.  Clear solutions were obtained even at the higher  concentrations  19 needed for  F nmr  studies.  This result excludes the p o s s i b i l i t y that  SnCSO^F)^ which i s v i r t u a l l y insoluble i n HSO^F may For K S n ( S 0 „ F ) o n l y a single 2 o  19  3 o  F nmr  l i n e at -41.37 ppm  downfield  could be found.  In addition  from CFCl^ used as an external standard  the signal for HSO^F i s found at -40.76 ppm, the p o s i t i o n i n the neat solvent. SO^F  have been formed.  v i r t u a l l y unchanged from  This finding excludes any  appreciable  exchange between solute and solvent at room temperature. The nmr  evidence points to a rather simple mode of i o n i z a t i o n  without appreciable condensation, polymerization  or d i s s o c i a t i o n .  For the three possible modes: HSO (1)  F  X Sn(S0 F). o  o  2  3 o  2X (solv) HSO  X Sn(S0 F). + HSO^F 2 3 6 3  (3)  X_Sn(S0_F), + 2HS0.F 3  (solv)  F 2X (solv) + HSn(SO.F), (solv) 3 o + SO F~(solv)  o  2  Sn(S0_F), J D  (2)  o  +  0  HSO F — 2 X  (solv) + H Sn(S0.F).(solv) o  2  3  j  b  + 2S0 F (solv) 3  X = C10  2  or K  the expected y values would be 0, 1 or 2 respectively. The observed value of ^0.5 HSn(S0„F), 3  o  2indicates an equilibrium with Sn(SO-F),,  as the dominant t i n species.  indistinguishable i n the nmr  spectrum may  3  and  b  The fact that both are be attributed to fast proton  - 146 -  exchange between the two ions.  It appears that the neutral acid  H Sn(S0„F)^ behaves as a good proton donor i n HS0 F. o  o  This i s not  surprising since HSbE^CSO^F)^"'"^ i s also a rather strong acid or 1  proton donor i n this solvent system. It must be concluded that the  hexakisfluorosulfatostannate(IV)  moiety can e x i s t i n solutions of strong protonic acids without appreciable  alteration.  - 147 -  CHAPTER VII REACTIONS OF LEWIS ACIDS WITH FLUOROSULFATES  A.  Introduction The reaction between CK> S0 F and Sn(S0 F> 2  3  3  4  f a l l s into the  general category of donor-acceptor reactions which proceed with complete anion transfer.  As i n most reactions of this type described i n the  l i t e r a t u r e only one type of anion, common to both the donor and the acceptor, i s present.  We decided to study a similar type of reaction  i n order to obtain i f possible  'mixed ligand complexes.  The most  l i k e l y acceptors would be SnF^, SbF,., AsF,. or BF and the donor of 3  choice, C10 S0 F, f o r the following reasons. 2  (1)  3  The C 1 0  + 2  cation i s well characterized and i s e.g. formed  readily i n the reaction of  187  FC10 2  +  o  AsF  c  5  >-  ClO.AsF, 2 6  ,  (2)  C10 S0 F has convenient physical properties for this purpose  (3)  the two anions F  2  3  and and S0 F 3  are expected to have similar  electronegativities. If may be noted that similar interactions of a f l u o r i d e donor with a  - 148 fluorosulfate as acceptor, e.g. FNC^ + SnCSO^F)^, had f a i l e d . There are very few relevant precedents for this type of compound. Anions of the [SbF (SO.F)^ ] n 3 6-n super acid solutions."'"^"'"  type have been i d e n t i f i e d i n so-called  They are evidently formed by SO^ i n s e r t i o n  into SbF,. and subsequent or concurrent solvent i n t e r a c t i o n with HSO^F.  B.  C10 SO^F Reactions  1.  C10„S0 F + SnF. 2 3 4  2  o  CK^SO^F reacts with SnF^ at room temperature to produce a gas, i d e n t i f i e d as C10  2  by infrared spectroscopy, and a yellow s o l i d shown  by i t s infrared spectrum to consist mostly of (C10 ) Sn(S0,jF)g. 2  C10  2  2  may well be formed from C10 F o r i g i n a l l y produced by reaction with 2  traces of moisture.  In this reaction approximately 3.09  g (18.1 mmoles)  of C10 S0 F were added to 0.832 g (4.27 mmoles) of SnF^ i n a one 2  3  part reactor i n the dry box. C10  2  o  and (C10 ) Sn(S0„F) plus some unreacted s o l i d , probably unreacted 2 2 3 6 o  o  SnF. or (CIO.)-SnF,.. 4 2 2 o 4.07  These two components reacted to produce  g.  The t o t a l weight of nonvolatile products was  This reacton was not investigated further once  (C10 ) Sn(S0 F)g 2  2  3  was i d e n t i f i e d as a major product, i n d i c a t i n g that this route would not 2lead to the expected S n F ( S 0 F ) 4  C10 S0 F + SbF 2  3  3  2  .  5  C10 S0 F reacted with SbF with the transfer of F 2  to SbF  5  3  5  from C10 S0 F  to produce C l O ^ b ^ ^ and SbF^SO.^ according to  C10„S0„F 2 3  +  3SbF 5 c  C10.Sb F 2 2 11 o  11  +  SbF.SO.F. 4 3  2  3  - 149 -  In a t y p i c a l reaction an excess of SbF,. was added to 1.021  g (6.14  mmoles) of C10 S0 F i n a two part reactor i n the dry box... The CK> S0 F 2  3  2  3  slowly dissolved i n the SbF,. and then reacted to produce a yellowish s o l i d and some clear, moderately v o l a t i l e l i q u i d . accomplished by d i s t i l l i n g o f f a l l v o l a t i l e s . i n the d i s t i l l a t e by comparing  SbF^SO^F was  identified  i t s properties and infrared spectrum  with those of SbF S0 F published by G i l l e s p i e , 4  Separation was  although there are some  7 1  3  discrepancies i n G i l l e s p i e ' s v i b r a t i o n a l spectra.  After a l l v o l a t i l e s  were removed i n vacuo at 40-50° f o r several days 3.19 g of a white s o l i d , m.p.  57-58° without decomposition, was obtained.  which was free of S0 F (test with B a C l 3  2  a f t e r hydrolysis) was  i d e n t i f i e d as C 1 0 S b F ^ by elemental analysis. 2  The s o l i d later  The elemental  2  analysis results are; calculated f o r C 1 0 S b F ^ , Sb, 46.74% and F, 2  2  40.31%, and found, Sb, 46.51% and F, 40.26%. The v i b r a t i o n a l spectral results f o r C K ^ S b ^ ^ are shown i n Table 41. v  1  The three v i b r a t i o n a l modes for C 1 0  + 2  are observed;  at 1050 IR and 1051 Raman, v 2 at 513 IR and 514 Raman and the v 3  doublet 1310 and 1295 IR and 1310 and 1294 Raman, i n agreement with previous work on C10  2  + 137 .  vibrations of the S b F ^  anion and are i n positions similar to those  2  found f o r XeFSbjF  187  ,  N  The remaining peaks would be assigned to  2 3 F  S b  2 ll' F  188 a n d  V  0  assignment i s given by Wiedlein and Dehnicke w i l l not be attempted here.  2 ll' 189  S 2  b  A  n  approximate  and further assignment  These spectra d i f f e r s i g n i f i c a n t l y from  the spectra of hexafluoroantimonates i n two respects. compounds exhibit no SbF^  189  F  The SbFg  vibrations above about 675 cm  1  even when  the symmetry of the anion i s lowered from 0^ by anion-cation interactions  - 150 -  Table 41.  V i b r a t i o n a l Spectra of C10 Sb F.^. 2  Infrared  Raman  1310 m  1310 m  1295 m  '  1294 w  Assignment  }  V  3  C 1  °2  <V  +  1150 w,br 1050 w  1051 s  v  CIO X  (v )  +  S  £-  702 m 690 vs,br  677 s  660 sh  647 s 626 w  590 w  595 m  513 s  514 m  495 m 290 s,br  305 w  v  2  C10  + 2  (6)  - 151 Table 42.  ONF Sb F 2  2  Vibrational Spectra of Sb^F  1 8 8 n  N F Sb F 2  3  6  1 8 8 n  a  n  d  s b F  g  XeFSb F 2  Salts.  1 8 7 1 1  Vt^Sb^ 765 730  725 695  699 680  665 614  693  705  682  700  662  685  654  523 278  298  296  275  284  225  220  BrF„SbF^ 2 6  183  ClF„SbF_ 2 6  678  662  641  644  183  KSbF,  661  596 552  542  523  537  575  493 284  292  294  282 270  267  278  183  189  - 152 and a l l SbF, 6  spectra have an absorption between 550 and 575 cm  1  which i s not seen i n any of the Sb F.^ complexes. 2  The f i r s t stage of the reaction of C K ^ S O ^ with SbF,. probably involves the transfer of S0 F from C10 S0 F to SbF to form C10 SbF S0 F 3  as an intermediate.  2  3  5  Either C10 SbF,.S0 F cleaves o f f S 0 2  3  subsequently react with another molecule of SbF,.  C10_SbF S0 F 2 5 3 c  Z  *•  o  ClO-SbF,  +  +  C10 SbF 2 6 o  SbF 5  *~  c  D  SO. 3  2  SbF 5  >-  c  +  £  7 1  3>  5  which may  according to  S0 3 o  ClO.Sb-F.. 2 2 11  SbF.S0„F 4 3  anion replacement may take place:  C10 SbF S0.F 2 5 3 o  +  c  C10 SbF, 2 o  +  o  SbF 5  >-  c  SbF_ 5  ->•  C10„SbF, + 2 6  SbF.S0„F 4 3  ClO-Sb.F.,., 2 2 11  or C10 SbF^S0 F may react with another SbF,. molecule p r i o r to S0 2  3  cleavage: C10 SbF_S0 F 2 5 3 o  +  o  SbF' 5  =»-  ClO.Sb.F. „S0 F 2 2 10 3 o  C10 Sb F S0 F  ^  C10 Sb F  S0  >-  SbF S0 F  2  3  2  +  10  SbF  3  5  2  4  2  3  n  +  S0  3  3  3  - 153 -  The reaction with CK^SO^F i n excess was subsequently attempted but removal of a l l r e s i d u a l CIO SO^F after reaction had occurred was not possible even with prolonged pumping.  However no SbF^SO^F or SO^  could be detected i n d i c a t i n g that neither of these possible byproducts was produced.  A more f e a s i b l e route to ClO^SbF^SO^F could possibly  be the reaction of C10„F with SbF.SO.F but this reaction was considered 2 4 3 beyond the scope of this thesis.  3.  C 1 0 2 S 0 F + AsF 3  5  Gaseous arsenic pentafluoride reacts with CIC^SO^F to produce ClO2AsF._SO.jF.  For t h i s reaction a two part reactor was charged with  0.345 g (2.08 mmoles) of CH^SO^F i n the dry box, evacuated i n a vacuum l i n e , and then the f l a s k and vacuum l i n e were pressurized to 300 mm Hg with AsF,. at room temperature.  Over a period of about four hours  the red color of CK^SO^F slowly changed to yellow.  If the excess  AsF,. was removed and the remaining nonvolatile yellow l i q u i d cooled i n l i q u i d nitrogen a yellow glass was formed and on warming to room temperature  the glass c r y s t a l l i z e d , with the evolution of a small amount  of gas, to a yellow s o l i d .  0.721 g (2.20 mmoles) of CIO AsF S0 F 3  which melted at 38° to an orange l i q u i d was produced i n this reaction.  The composition was established by elemental analysis:  calculated f o r C10 AsF 5 S0 F, CI, 10.54%, F, 33.89% and S, 9.53% and 2  3  found, CI, 10.40%, F, 34.10% and S, 9.67%. The v i b r a t i o n a l spectra l i s t e d i n Table 43 indicate the presence of C 1 0 2 + , weakly bridging SO^F, and AsF^.  The CK^"** modes are i n the  same regions as found previously and the higher frequency AsF modes  - 154 -  Table 43.  Raman Spectrum f ClC^AsF^C^F. 0  Raman  Assignment  1359 s  VS0  1307 m 1291 w 1205 vs 1060 sh  3  V C10 3  VS0  + 2  3  1057 vs  v CIO 1 I  1034 w  vS0  +  3  856 w 849 m  vSF  700 s  vAsF  668 vs  vAsF  641 w 602 sh 596 m 559 m  v C10 3  524 s 451 sh 448 w 429 m 382 m 366 sh 353 s 315 m 298 sh 272 w  >remaini  + 2  (5)  - 155  T-  (the only ones which could be assigned with any certainty) are i n the 190 191 from comparisons to spectra of C10 AsF , AsF , 2 o _>  positions expected  o  192 and BrF(.. at 1034  The positions of the SO^F modes, p a r t i c u l a r l y the band  cm , are somewhat unusual. 1  This band which can only be  due  to the t h i r d SO,, stretching mode i s at higher frequency than would be 70 2expected for a monodentate SO^F  group (see e.g. BrSO^F  or Sn(S0.jF)g  complexes) and i s rather reminiscent of the lowest frequency SO^ i n bidentate compounds (see Table 25). This suggests that the group may  be weakly bridging between the AsF,. and C10  SO^F  groups, i . e .  2  that there i s some anion-cation i n t e r a c t i o n between the C 1 0 the fluorosulfate group.  stretch  + 2  and  Anion-cation interactions have been postulated  previously for C 1 0 compounds on the basis of anion dependent Cl-0 stretching modes and non-zero quadrupole s p l i t t i n g i n the Mossbauer 137 spectrum of (C10„)_SnF^. However, the s h i f t i n g of the S0 stretch 2 2 o J -1 2by approximately 25 cm from i t s p o s i t i o n i n Sn(S0„F), compounds +  2  o  j  o  i s perhaps too small to allow d e f i n i t e conclusions. 19 The  F nmr  spectrum of C10 AsF,.S0 F i n HS0..CF shows two 2  3  3  environments i n addition to the solvent resonance. downfield for CFC1 are found +49.1  3  at -40.3  ppm  i s i n the region i n which fluorosulfate fluorides  (HS0.-F i s -40.7  ppm,  One  fluorine  ppm)  and the other, a broad resonance at  i s due to the fluorines on arsenic.  No fine structure was  detected at room temperature. 4.  C10 S0 F + 2  3  BF  3  A reaction similar to the reactions of C10 S0 F with SbF^ 2  AsF,. was  attempted with C10 S0.-F and BF 2  3  3  and  by adding a 300 mm Hg pressure  - 156 -  of BF^ to CIO SOgF at room temperature but there was no evidence of reaction.  The same reactants were mixed overnight at -78° using 550  Hg pressure of BF^ and 0.455 g (2.74 mmoles) of CK^SO^F.  mm  Some orange  coloured s o l i d which melted at -25° to a red l i q u i d was produced.  At  room temperature 0.498 g of red l i q u i d remained after a l l v o l a t i l e s 2.74 mmoles of ClO2BF.jSO.jF would weigh 0.640 g.  were removed.  This  suggests that either very l i t t l e reaction occurred or the product i s unstable at room temperature and decomposed to C102S0 F and BF^. 3  Only  BF^ was detected by IR i n the gas phase.  C.  KS0 F + 3  SbF  5  The reaction of KSO^F with SbF^ also produced some unusual results. When an excess of SbF,. was added to 0.681  g (4.94 mmoles) of KSO^F i n  the dry box and the solution was allowed to react f o r two days a white, crystalline,  moderately hygroscopic s o l i d which was insoluble i n the  excess SbF,. and  melted over the broad range of 110-130° was  produced.  The l i q u i d phase was shown by i t s IR spectrum to contain SbF^SO^F.  71  The IR spectrum of the s o l i d indicated that i t contained unreacted KS0 F, KSbFg (confirmed by the presence of SbF^SO^ i n the l i q u i d ) and 3  some compound containing covalent f l u o r o s u l f a t e groups.  The  S0  3  stretching frequencies of this covalent f l u o r o s u l f a t e are found at 1410,  1220 and 1012) cm"  and the S-F stretch at 822 cm" .  1  peaks at 582 and 554 cm  1  1  would possibly be S0  3  The weaker  deformation modes.  Reactions of KS0 F and SbF<. f o r shorter periods of time also 3  produced both s o l i d products.  - 157 D.  BrSO^F and BrCSO^F)  Reactions  BrSO^F reacts with either a d e f i c i t or an excess of SbF,. to produce a deep red coloured l i q u i d and no very v o l a t i l e or s o l i d p r e c i p i t a t e s .  byproducts  This red colour i s c h a r a c t e r i s t i c of the  B r  2  +  193 cation.  An infrared spectrum of the red l i q u i d formed i n the  reaction of BrSO^F and excess SbF^ was recorded and i t indicated the presence of both bidentate SO^F and possibly monodentate SO^F as well as SbF . x Br(SO.jF) reacted with SbF 3  c  to produce a pale yellow coloured  solution from which white crystals slowly separated.  When an excess  ;(15.;4gg,;71.0 mmoles) of SbF was d i s t i l l e d onto 3.80 g (10.1 mmoles) 5  of Br(S0.jF) a reaction occurred with gas evolution to produce a brown 3  coloured intermediate solution and then a yellow solution.  When the  excess SbF,. was removed at 50° no c r y s t a l l i z a t i o n occurred and 5.51 g (10.7 mmoles i f Br(S0 F)„SbF ) of the yellow solution remained. 3  2  On  6  standing for several days some s o l i d precipitated out, however, attempts to separate this s o l i d were unsuccessful.  SbF^SO^F was  i d e n t i f i e d by i t s IR spectrum i n the l i q u i d removed from the reactor. A Raman spectrum, Table 44, of the nonvolatile yellow l i q u i d was recorded.  This spectrum shows Br^O^F^"*" peaks very similar to those + 179 of the cation i n [Br(S0„F)„]„Sn(S0„F). and Br(S0 F). /super acid 3 2 2 3 o 3 2 and SbF." bands at 660, 564, 299, and 283 cm" indicating that o Br(S0„F)„SbF. i s present i n the l i q u i d . 3 2 o o  1  - 158 -  Table 44. Raman Spectrum of Br(SO F) SbF  Mode 1514 m  Assignment  V  a °2  V  s  S  1425 vw 1254 s  , S 0  2  1080 w 985 w  vSO  897 w,sh 875 m  vS-F  720 vs  v Br-0 a  705 w, sh  (v±)  660 vs  vSb-F  616 w 564 s  v Br-0 s vSb-F ( v )  530 w, sh  S0  468 m  SOBr bend  435 w  SF wag  320 w  SOBr wag  299 w  SSb-F  283 w  6Sb-F  230 w, sh  2  2  rock  }  ( v  - 159  -  CHAPTER VIII GENERAL CONCLUSIONS  A.  Summary The application of two  simple synthetic methods, the acid  s o l v o l y s i s of organotin(IV) chlorides by strong protonic acidsj i n p a r t i c u l a r f l u o r o s u l f u r i c acid, and the rather unique n o n s t a t i s t i c a l r e d i s t r i b u t i o n reactions of organotin(IV) chlorides with fluorosulfates, has resulted i n the preparation of novel methyltin(IV) chloride sulfonates.  The second method, ligand scrambling, could also be extended  to reactions of Sn(SO.jF) with tin(IV) halides r e s u l t i n g i n several 4  tin(IV) fluorosulfate derivatives. was  observed and the s t r u c t u r a l l y interesting compound  with possibly tetradentate The  i n SnCl^ 6  fluorosulfates was  2-  The  [Sn(SO F) ] J o  2-  ion.  Ti^Cl^(SO..F)^  obtained.  Ligand substitution of CI  by SO„F using S 0 F provided an alternative route to this 3 262 J  surprising thermal s t a b i l i t y of the  stannate ion allowed the formation of the new cations I (SO^F) 2  +  and Br(S0.-F)2 . +  hexakisfluorosulfato halogen b i s f l u o r o s u l f a t o  Attempts to obtain these and  cations resulted i n the i d e n t i f i c a t i o n of the anion [AsF^SO^F] offshoot  transfer  investigation of the complexing a b i l i t y of Sn^O^F)^ resulted  i n the detection of the  ion.  With T i C l ^ , complete SO.-F  of the o r i g i n a l study.  similar i n an  - 160 -  Besides occasional solution studies of interesting solutes i n 119 HSO^F our primary interest focussed on the use of  Sn Mossbauer  spectroscopy, Laser Raman spectroscopy and infrared spectroscopy i n elucidating the i d e n t i t i e s and structures of the compounds synthesized. Two basic s t r u c t u r a l types emerged. The f i r s t was trans octahedral b i s f l u o r o s u l f a t e s (and other related sulfonates) of the type XYSn(S0 F) 3  2  (X, Y = CH<, CI, Br, F, and S0 F) 3  3  with the fluorosulfate groups functioning as bidentate bridging groups with coordination through oxygen.  This postulate was o r i g i n a l l y based  on v i b r a t i o n a l c r i t e r i a such as the apparent symmetry lowering from C ^ to C r e s u l t i n g i n an increase from s i x to nine fundamentals a l l found s in well defined postions and was l a t e r confirmed by an X-ray d i f f r a c t i o n 135 study of ( C H ) S n ( S 0 F ) . 3  2  3  2  These results together with the Mossbauer  data allowed good insight into the bonding i n these compounds.  The  postulated model using 3 center 4 electron bonds and 5p and 5p o r b i t a l s x y on t i n for tin-oxygen bonding leaving a 5s5p hybrid o r b i t a l f o r bonding z to X and Y, i s consistent with both the X-ray d i f f r a c t i o n results and the Mossbauer parameters.  Correlations such as between the electronegativ-  i t i e s of the ligands X and Y with the observed isomer s h i f t s and between their Taft inductive constants and the quadrupole s p l i t t i n g s were rather successful. The second group, supposedly trigonal bipyramidal monofluorosulfates (and other sulfonates) of the type X YSnS0 F (X, Y = CH 2  3  3>  CI), could be  r a t i o n a l i z e d as having bidentate bridging fluorosulfates as before. Results f o r these compounds could not be correlated nearly as well because a tendency  towards hexacoordination around t i n v i a p o t e n t i a l l y  - 161 -  bridging chloride ligands w i l l cause d i s t o r t i o n s . Structural evidence  for  Sn(SO_F)., 3  2-  b  rests primarily on Mossbauer  r e s u l t s , i n p a r t i c u l a r on the absence of any quadrupole s p l i t t i n g .  The  v i b r a t i o n a l spectra, i n p a r t i c u l a r for [X(SO„F)„]„Sn(SO„F), compounds, i l l j o are rather complex and defy any rigorous assignment i n the SO^F stretching and bending regions. As i s so often the case i n the stereochemistry of tin(IV) and organotin(IV) compounds, the "normal" coordination number of four was not found f o r any of the newly synthesized compounds.  B.  Suggestions f o r Further Work A number of p o s s i b i l i t i e s f o r expansion emerge as a result of this  study, some of which are currently investigated.  These p o s s i b i l i t i e s  are mentioned here i n no p a r t i c u l a r order. (1)  The extension of protonic acid s o l v o l y s i s to other suitable  organometallic derivatives of some main group elements such as Ge, Pb, Sb, or B i may be contemplated.  The use of other organotin(IV) halides with  larger a l k y l groups, v i n y l groups or aromatic groups has been p a r t i a l l y explored i n connection with this study 143 2 2 "  H P 0  F  a S  (2) fruitful.  143  as has the use of HF  142  or  a c i d s  The use of similar ligand r e d i s t r i b u t i o n reactions may prove Recently completed work on ligand rearrangement reactions of 153  titanium(IV) chloride-sulfonates (3)  supports this view.  The i d e n t i f i c a t i o n of bidentate bridging sulfonate groups i n  other systems should be f a c i l i t a t e d . may serve as an example here.  The v i b r a t i o n a l study of Ga(SO.jF)  194 3  - 162 -  (4)  Refinement of the Mossbauer data by experimental determination  of the sign of the e l e c t r i c f i e l d gradient  tensor i s necessary as a  basis for detailed point charge calculations and to a r r i v e at a more d e f i n i t e view on the supposedly t r i g o n a l bipyramidal  compounds.  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