Author:
Galligan Janine K.,Happer D. Alan R.,Wilson Gareth R. S.
Abstract
(Me3Si)3CSi(CD3)2I, (Me3Si)3CSi(CD3)2Br, and (Me3Si)3CSi(CD3)2H solvolyze in refluxing acetic acid in the presence of HgX2 to give, in addition to (Me3Si)3CSi(CD3)2X and (Me3Si)3CSi(CD3)2OAc, isomers with structures (Me3Si)2C(SiMe2X)Si(CD3)2Me and (Me3Si)2C(SiMe2OAc)Si(CD3)2Me. The first two also react if AgX is used in place of HgX2, but (Me3Si)3CSi(CD3)2H is inert. In refluxing trifluoroacetic acid (Me3Si)3CSi(CD3)2I and (Me3Si)3CSi(CD3)2H solvolyze even in the absence of a catalyst to give similar products. The products distributions are believed to arise from nucleophilic attack on a methyl-bridged cationic intermediate.