Rhodium‐catalyzed silylative coupling of olefins with vinylsilanes

RhH(CO)(PPh33 appeared to be a very effective catalyst for disproportionation of vinylsilanes and their co‐disproportionation with styrene and 1‐decene. The insertion of vinylsilane (or bis(silyl)ethene) into the Rh–H bond followed by β‐silyl transfer to form a Rh–Si bond and elimination of ethylene (or vinylsilane), in combination with a MS study of the product of the reaction of styrene‐d8 with vinylsilane and well‐known insertion of alkene into the Rh–Si bond accounts for a non‐metallacarbene mechanism of a new rhodium‐catalyzed silylation of olefins with vinylsilanes.