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SPECTROSCOPIC STUDIES OF TIN( IV) AND MIXED OXIDATION .STATE TIN( I I)TIN( IV) COMPOUNDS
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By
JAMES PATRICK JOHNSON, B.Sc.
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A Thesis
Submitted to the Faculty of Graduate Studies
in Partial Fulfilment of the Requirements
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for the Degree
Doctor of Philosophy
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McMaster University
June 19B3
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SPECTROSCOPIC STUDIES OF TIN(IV) AND
TIN(II)TIN(IV) COMPOUNDS
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DOCTOR OF PHILOSOPHY (19B3)
McMaster University
(Chemistry)
Hamilton, Ontario
TITLE:
Spectroscopic' Studies of Tin(IV) and Mixed
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Ox~dation
State Tin(II)Tin(IV) Compounds
AUTHOR:
James PatriGk Johnson, B.Sc.
SUPERVISOR:
Professor T. Birchall
(McMaster
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NUMBER OF PAGES: xvi; 202
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Univer~ity)
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ARSTRACT
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hexamethylditin and tetramethyltin with fluorosulfuric
aci~.
T~e
tetramethylditin dication [(CH3)4sn22+] is proposed as an intermediate in
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the suggested reaction sequence ·for the,solvolysis of hexamethylditin
with fluorosulfuric acid.
The reaction between hexamethylditin and a series of carboxylic
acids has heen investigased.
Compounds of empirical formula
(CH 3) 2Sn(02CR) were prepared-'and formul ated as the tetramethyl dffin
carboxylates, (CH3)4Sn2(02CR)2'. Infrare"d, Raman, 1H and 13C n.m.r. and
1~9Sn ~ssbauer data are presented for this series of compounds.
The compounds have been' shown to have a tetramet"hylditin moiety in which'
the carhoxylate ligand pridges both tin atoms.
The X-ray crystal
structure of three of these compounds [R '" CH~Cl, eC1
and CF ] are
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presented and the spectroscopic data evaluated in 1ight of the crysta 110graphic data.
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The X-ray crystal structure of
{[(CH3)2Sn(O~CCF3)]O}2
is
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also presented.
The solvolysis of hexaphenylditin by a series of carboxylic acids
was investigated.
Seven nove1C~mpounds of empirical formula Sn(02CR)3
were synthesized.
Infrared, Raman and 119Sn ~dssbauer spectra
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are reported f~~ the series of Sn(02CR)3 compoundi which are best
formulated as [Sn(II)Sn(.IV)O(02CR)40(OeR)~]2'
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119Sn M6ssbauer data for
./.
5n(02CR)4' are also pres:nted.
The X-ray crystal structure of
[5n( I [)5no( IV)O(02CCF3)4]2C6H6 has been determined and its relationship to
other mixed oxidation, state tin carboxylates examined.
The solvolysis of hexaphenylditin by
inorqa~ic
acids has been
investigated., 11gSn Mllssbauer spectra are presented for the
products and vibrational (infrared and/or Raman) data for the isolated
solids.
Compounds of empirical formula SnF , Sn(S03CF3)3 and
3
Sn(IV)O·S04Sn(II)(SOl)2 are formulated a's the polymers
[Sn(II)Sn(IV)F 6]x' [Sn(II)5n(IV)(S03CF3)6]x and
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[Sn(I-V)O.S04 Sn (II)(SOl)2] "The Sn(50 3R)3 compounds where R = CH 3 , C2HS
x ~
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and OH were not isolated free of excess~cid. I1gSn MOssbauer
spectroscopy also showed that these
and the formulation of
~roducts
contain tin(II) and tin(IV)
[Sn(II)Sn(IV)(S03~)6]x is
suggested.
The ~nteraction of SnF 2 with Sn(S03CF3)~ produced Sn3F2(S03CF3)6"
119 Sn MOssbauer data together with infrared and Raman data have
been interpreted in terms of a cpmpound of formulation
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ACKNO~LEDGEMENTS
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The author wishes to thank his research director,
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Professor T. Birchall for his sincere interest, patience and guidance
during the course of this work.
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Special thanks are also due to Dr. I. D. Brown and
'Mr. R. Faggiani who provided the X-ray structural data for some of the
compounds.
Thanks are also due to the technical staff in the Department
of Chemistry for
The
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a~thor
thei~
assistance and maintenance of the instruments.
gratefully acknowledges Mrs. E. Denham, Word Processing
Centre, Faculty of Science,
fo~
her swift typing of this thesis.
The
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author wishes to thank Dr. J. G. Ballard for his assistance in the early
stages of this work.
The author also'wishes to thank Dr. R. D.
~yers
and
Mr. R. Batchelor for their friendship.
Financial assistance from McMaster University from 1974 to 19BO
is
J
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9r~tefully
acknowledged •.
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Finally the author wishes to thank his wife, Trudy, for her
encouragement and. support during the final stages of this work.
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TO MY MOTHER AND FATHER
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TABLE OF CONTENTS
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CHAPTER ONE
I NTROOUCTI ON
A. General
B.
CHAPTER-TWO
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Sn
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Spectroscopy
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EXPERIMENTAL
A.' General Experimental Techniques
(i)
Vacuum System
(i i)
Ory Atmosphere System
(iii)
Reaction Vessels
B. Experimental Techniques and Apparatus
(i)
~ssbauer Spectrometer
(ii)
Laser Raman Spectrometer
(i i i)
Infrared Spectrometer
(iv)
X-ray Crystallography
(v)
Nuclear Magnetic Resonance Spectroscopy
(vi)
Chemical Analysis
C. Purification and Preparation of Starting
yO Materials
I. Reagents
(i)
Hexamethylditin
(ii) Hexphenylditin
(iii) Tetraphenyltin and Tetramethl'ltin
(iv) Acids and Ar]hydrides
II. Solvents
(i)
Chloroform and Chloroform-d
(ii) Sulphur Dioxide
(iii) Benzene
(iv) Tetrahydrofuran
D. Preparations
(it
C4H6F D2Sn. (CH3)2Sn(02CCF3)
3
(ii)
C H F 0 Sn, (CH3)2Sn(02CCHF2)
4 7 2 2
~(iii)
C4H C1 30 Sn. (CH3)2Sn(02CCC13)
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2
(iv)
C H C1 0 Sn, (CHJ)2Sn(02CCHC12)
4 7 2 2
(v)
C4HSC10 2Sn, (CH3)2sn(02CCHP)
9
~ssbauer
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If!
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lCl
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(v i)..
(vii)
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( i x)
( x)
(xi)
2fi
( xii)
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(xiii)
(xiv)
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27
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28
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29
(x v)
(xvi)
>(xvii)
(xviii)
(xi x)
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30
( xx)
(xxi)
(xxi i)
(xxiii)
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CHAPTER THREE -- ACID SDLVDLYSIS OF HEXAMETHYLDITIN AND
TETRAPHENYLTIN
A. General Introduction
B. Results and Discussion
(i)
Tetramethyltin and hexamethylditin
in HS03F
C. Bis(haloacetato)-bis[dimethyltin(IV)]:
"Tetramethylditin Carbo1<ylates"
(i)
Introduction
D. Results and Discussion
(i)
Preparation and Chemical Properties
(ii)
Vibrational Spectra.
(i ii)
Tin-llq rilssbauer Spectra
(iv)
Nuclear Magnetic Resonance Spectra
r~ecllanism of toe Formation of
(v)
(CH3)4Sn2(02CR)2
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CHAPTER
FOU~
-- THE CRYSTAL STRUCTURES OF (CH3)4Sn2(02CCC13)2'
(CH 3) 4Sn 2( 0 2CCH
2' (CH 3) 4Sn 2( 0 CF 3) 2'
{[(CH3)2Sn(02CC~3)]0)2 and
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{[(CH3)2Sn(02CCCl3)]Ol2
A. IntroductlOn •
8. Experimental
(i)
The Crystal Structure Data for
Bis(u-trichloroacetato-O,O' )'bis[dimethyltin(IV)]"
(i i)
The Crystal Structure Data for
8is(u-trifluoroacetato-O,O')- ,
bis[dimethyltin(IV)] and (u-monochloro>
acetato-O,O')-bis[dimethyltin(IV)]
C. Discussion
D. Crystal Structure of {[(CH~2Sn(02CCF~2QL
and {[(CH~2Sn(02CCCI ~2Q[
(i)
Introduction.
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(ii)
Crystal Structure Data for Di-u3-oxo-
P)
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bis(u-trif~oroacetato-O,O')-
(iii)
(i,v)'
CHAPT~
FIVE
bi s( t ri fl uo roacetato) t et raki-s[dimethyltin(IV)] and Di-u -oxo-bis(u3
t ri fl uoroacetato -0,0' ) -b i s( t ri ch 1 oroacetato)tetrakis[dimethyltin(IV)]
Preparation and Chemical Properties
Di scussion of the Crystal and
Molecular Structure of
{[(CH3)2Sn(02CCF3)]0)2
ACID' SOLVOLYSIS OF HEXAPHENYLDITIN AND
TETRAPHENYL T! N
A. Introduction
8. Results and Discussion
(i)
Preparation and Chemical Properties
(i i)
Ti n-119 Mllssbauer Data
(i i i)
Ti n( I 1) Mllssbauer Regi on
(iv)
Ti n( IV) Mllssbauer Region
(v)
Temperature Dependent tilssbauer
Effect
(vi)
Vibrational Data
Mechanism of Format jon of
(v i i )
[Sn(II)Sn(IV)O(02 CR )4 0 (OCR)2]2
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101
105
116
122
126
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