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Date of Award

6-1983

Degree Type

Thesis

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

Supervisor

Professor T. Birchall

Abstract

Proton n.m.r. data are presented for the solvolysis of hexamethylditin and tetramethylt in with fluorosulfuric acid. The tetramethylditin dication [(CH₃)₄Sn₂²⁺] is proposed as an intermediate in the suggested reaction sequence for the solvolysis of hexamethylditin with fluorosulfuric acid.

The reaction between hexamethylditin and a series of carboxylic acids has been investigated. Compounds of empirical formula (CH₃)₂Sn(O₂CR) were prepared and formulated as the tetramethylditin carboxylates, (CH₃)₄Sn₂(O₂CR)₂. Infrared, Raman, ¹H and ¹³C n.m.r. and ¹¹⁹Sn Mössbauer data are presented for this series of compounds. The compounds have been shown to have a tetramethylditin moiety in which the carboxylate ligand bridges both tin atoms. The X-ray crystal structure of three of these compounds [R = CH₂Cl, CCl₃ and CF₃] are presented and the spectroscopic data evaluated in light of the crystallographic data. The X-ray crystal structure of {[(CH₃)₂Sn(O₂CCF₃)]O)₂ is also presented. The solvolysis of hexaphenylditin by a series of carboxylic acids was investigated. Seven novel compounds of empirical formula Sn(O₂CR)₃ were synthesized. Infrared, Raman and ¹¹⁹Sn Mössbauer spectra are reported for the series of Sn(O₂CR)₃ compounds which are best formulated as [Sn(II)Sn(IV)O(O₂CR)₄O(OCR)₂]₂. ¹¹⁹Sn Mössbauer data for Sn(O₂CR)₄ are also presented. The X-ray crystal structure of [Sn(II)Sn(IV)O(O₂CCF₃)₄]₂C₆H₆ has been determined and its relationship to other mixed oxidation state tin carboxylates examined.

The solvolysis of hexaphenylditin by inorganic acids has been investigated. ¹¹⁹Sn Mössbauer spectra are presented for the products and vibrational (infrared and/or Raman) data for the isolated solids. Compounds of empirical formula SnF₃, Sn(SO₃CF₃)₃ and Sn(IV)O·SO₄Sn(II)(SO₃F)₂ are formulated as the polymers [Sn(II)Sn(IV)F₆]ᵪ, [Sn(II)Sn(IV)(SO₃CF₃)₆]ᵪ and [Sn(IV)O∙SO₄Sn(II)(SO₃F)₂]ᵪ. The Sn(SO₃R)₃ compounds where R = CH₃, C₂H₅ and OH were not isolated free of excess acid. ¹¹⁹Sn Mössbauer spectroscopy also showed that these products contain tin(II) and tin(IV) and the formulation of [Sn(II)Sn(IV)(SO₃R)₆]ᵪ is suggested.

The interaction of SnF₂ with Sn(SO₃CF₃)₃ produced Sn₃F₂(SO₃CF₃)₆. ¹¹⁹Sn Mössbauer data together with infrared and Raman data have been interpreted in terms of a compound of formulation [(Sn(II)SO₃CF₃)₂Sn(IV)F₂(SO₃CF₃)₄]ᵪ.

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