Scope and mechanism of the intermolecular addition of aromatic aldehydes to olefins catalyzed by Rh(I) olefin complexes.

Rhodium (I) bis-olefin complexes CpRh(VTMS)(2) and CpRh(VTMS)(2) (Cp = C(5)Me(5), Cp = C(5)Me(4)CF(3), VTMS = vinyl trimethylsilane) were found to catalyze the addition of aromatic aldehydes to olefins to form ketones. Use of the more electron-deficient catalyst CpRh(VTMS)(2) results in faster reaction rates, better selectivity for linear ketone products from alpha-olefins, and broader reaction scope. NMR studies of the hydroacylation of vinyltrimethylsilane showed that the starting Rh(I) bis-olefin complexes and the corresponding Cp*/Rh(CH(2)CH(2)SiMe(3))(CO)(Ar) complexes were catalyst resting states, with an equilibrium established between them prior to turnover. Mechanistic studies suggested that CpRh(VTMS)(2) displayed a faster turnover frequency (relative to CpRh(VTMS)(2)) because of an increase in the rate of reductive elimination, the turnover-limiting step, from the more electron-deficient metal center of CpRh(VTMS)(2). Reaction of Cp/Rh(CH(2)CH(2)SiMe(3))(CO)(Ar) with PMe(3) yields acyl complexes Cp*/RhC(O)CH(2)CH(2)SiMe(3)(Ar); measured first-order rates of reductive elimination of ketone from these Rh(III) complexes established that the Cp ligand accelerates this process relative to the Cp* ligand.