Reactions of peroxides with hexaethyldistannane and hexaethyldisilane

Summary

• 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.