Halomethyl—metal compounds XXXVIII. Reactions of phenyl(trihalomethyl)mercury compounds with bis(trimethylsilyl)- and bis(trimethylgermyl)mercury

Abstract

The reaction of phenyl(bromodichloromethyl)mercury-derived dichlorocarbene with bis(trimethylsilyl)mercury in benzene at 80° gave as principal products trimethyl(trichlorovinyl)silane, trimethylchlorosilane, metallic mercury and phenylmercuric bromide. An analogous reaction with bis(trimethylgermyl)mercury gave trimethyl(trichlorovinyl)germane and trimethylchlorogermane. The same reactions were found to occur between phenyl(dibromochloromethyl)- and phenyl(tribromomethyl)mercury and bis(trimethylsilyl)mercury, but the yields of the (trihalovinyl)silanes, Me 3SiCClCClBr and Me 3SiCBrCBr 2 respectively, were much lower. Experimental evidence was gathered which indicated that these reactions proceed via dihalocarbene insertion into the Group IV element-to-mercury bond followed by another CX 2 insertion into the newly formed HgC bond in the Me 3MCX 2Hg intermediate and subsequent β-elimination of HgX from Me 3MCX 2CX 2Hg species thus formed. Among the evidence presented was the finding that the reaction of PhHgCCl 2Br-derived dichlorocarbene with Me 3SiCCl 2Hg compounds gives Me 3SiCClCCl 2.