An easy, direct and room temperature silicon–carbon bond activation is reported. The reaction of [RhCl(coe)2]2 with the silane Si(Me)2(o-C6H4SMe)2 in the presence of an halide extractor provokes a Si–CH3 bond cleavage yielding a cationic silyl-methyl–Rh(III). In contrast, if the reaction is performed using the Rh(I) bis-alkene dimers, [RhCl(cod)]2 or [RhCl(nbd)]2, the Si–CH3 bond activation does not occur.
