Organosilicon chemistry. Part III. The reaction of bis(trimethylsilyl)mercury with aryl halides

Abstract

Bis(trimethylsilyl)mercury, prepared in improved yield by reaction of sodium amalgam with iodotrimethylsilane, reacts with aryl bromides at 190° to give the diarylmercury, bromotrimethylsilane, aryltrimethylsilane, and hexamethyldisilane as the major products. The formation of the diarylmercury, followed by its relatively slow decomposition, accounts satisfactorily for the formation of biaryls without the need to postulate free trimethylsilyl radicals. The slower reactions of bis(trimethylsilyl)mercury with aryl chlorides, and the rapid room temperature reaction with iodobenzene to give diphenylmercury, iodotrimethylsilane, trimethylphenylsilane, and phenyl mercuric iodide are also consistent with initial formation of aryl(trimethylsilyl)mercury. Free trimethylsilyl radicals, which are involved in the main reactions to a much less extent than postulated by earlier workers, are probably responsible for the formation of trimethylsilane in the high temperature reactions.