Reactions of peroxides with hexaethyldistannane and hexaethyldisilane

Abstract

1. The reaction of t-butyl peroxide with hexaethyldistannane was investigated. The reaction products were methane, ethane, butane, t-butyl alcohol, t-butoxytriethyltin, decaethyltetrastannane, and organotin compounds containing chains of metal atoms. A free-radical mechanism is proposed for the reaction. 2. Compounds of the homologous series (C2H5)3Sn[Sn(C2H5)2]n Sn(C2H5)3 and their branched isomers undergo disproportionation with formation of tin and tetraethyltin when heated with catalytic amounts of aluminum chloride, and this can serve as a qualitative reaction for the Sn-Sn bond. Taking hexaethyldistannane and decaethyltetrastannane as examples, we showed that the disproportionation reaction can be used for the determination of the molecular weights of compounds of this kind. 3. Under ultraviolet irradiation tetraethyltin eliminates ethyl radicals and is converted into complex colored compounds containing metal-metal bonds. 4. A study was made of the reactions of benzoyl and t-butyl peroxides with hexaethyldilsilane, which proceed by free-radical mechanisms. The Si-Si and Si-C bonds in this compound are stable to homolytic cleavage. The radicals formed by the breakdown of the peroxides abstract hydrogen from the ethyl groups of hexaethyldisilane. The silicon-containing radicals then formed later recombine.