Supported Electrophilic Organoruthenium Catalyst for the Hydrosilylation of Olefins

A series of supported electrophilic organoruthenium complexes has been synthesized via surface organometallic chemistry (SOMC) techniques and applied to the selective hydrosilylation of olefins. The air-sensitive 16e<sup>-</sup> complex Cp*RuMes(PCy<sub>3</sub>) (1) (Cp* = pentamethylcyclopentadienyl, Mes = mesityl) was synthesized by the treatment of Cp*RuCl(PCy<sub>3</sub>) with mesityl Grignard MesMgBr. This species was chemisorbed onto sulfated zirconia SO<sub>4</sub>/ZrO<sub>2</sub>, but the resulting material was inactive toward cyclohexene hydrosilylation with phenylsilane. Instead, Cp*RuMes(PCy<sub>3</sub>) was treated with phenylsilane (PhSiH<sub>3</sub>) to provide a ruthenium disilyl hydride complex Cp*RuH(SiH<sub>2</sub>Ph)<sub>2</sub>(PCy<sub>3</sub>) (3), which was fully characterized by NMR spectroscopy and single-crystal X-ray diffraction. Grafting this species onto SO<sub>4</sub>/ZrO<sub>2</sub> resulted in the formation of phenylsilane along with the surface electrophilic species [Cp*RuH(R)(X-SiHPh)(PCy<sub>3</sub>)] (R = H, O<sub>3</sub>S-O or O<sub>3</sub>Zr-O; 4a, 4b, X = O<sub>3</sub>S-O, and O<sub>3</sub>Zr-O, respectively) as the major species. Material 4 was characterized via a combination of spectroscopic techniques including dynamic nuclear polarization (DNP)-enhanced solid-state NMR spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray absorption spectroscopy (XAS), and density function theory (DFT) calculations. Further, capping the remaining acid sites on 4 with Me<sub>3</sub>Si-SiMe<sub>3</sub> provides 5, which significantly reduces side reactions, such as olefin isomerization and silane redistribution. Catalyst 5 is a highly robust and selective hydrosilylation catalyst and can be recycled up to 5 times without significant diminishment of activity. Exclusive anti-Markovnikov regiochemistry, cis-addition selectivity, and the inactivity of secondary and tertiary silanes provide support for the proposed Glaser-Tilley mechanism involving cationic ruthenium silylene species analogous to homogeneous systems.