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UBC Theses and Dissertations

The synthetic and spectroscopic study of some new tin (IV) and organotin (IV) fluorine compounds Levchuk, Larry E.

Abstract

The solvolysis of methyltin(IV) chlorine compounds of the general type (CH₃)nSnCl₄₋n with n ranging from 0 to 4, is studied in aqueous and anhydrous hydrogen fluoride under a variety of conditions. The studies in anhydrous HF have resulted in the synthesis of the new compounds methyltin(IV) trifluoride, dimethyltin(IV) chloride fluoride and methyltin(IV) dichloride fluoride. Methyltin(IV) chloro difluoride could not be synthesized in this way. A special monel reflux reactor was utilized for these reactions. Attempts to solvolyze vinyl- and phenyltin compounds with anhydrous HF did not yield pure products. In these cases, the evidence indicates that cleavage of the Sn-Cl and Sn-C bonds occurs in an unpredictable manner. A convenient method for the preparation of SnCl₂F₂ is found in the solvolysis of SnCl₄ with anhydrous HF. Interaction of this compound with either S₂O₆F₂ or C1OSO₂F results in the formation of SnF₂(SO₃F)₂. Attempts to find alternative synthetic routes to SnF₂(SO₃F)₂ were unsuccessful. Structural proposals for these compounds are based on infrared, Raman and ¹¹⁹Sn Mössbauer spectra. All the new compounds are found to be polymeric via fluorine or fluorosulphate bridges, resulting in penta- or hexacoordination around tin. Dialkyltin(IV) difluorides are easily obtained when the corresponding chlorides are solvolyzed in aqueous hydrogen fluoride. Dimethyltin, diethyltin, dipropyltin, dibutyltin and dioctyltin difluorides are prepared in this way. However, divinyltin(IV) difluoride and diphenyltin(IV) difluoride cannot be made via this route. Also, CH₃SnF₃ and the methyltin(IV) chloride fluorides cannot be synthesized from solvolysis reactions involving aqueous HF.

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