Experimental and Computational Studies of the Ruthenium-Catalyzed Hydrosilylation of Alkynes: Mechanistic Insights into the Regio- and Stereoselective Formation of Vinylsilanes

The ruthenium hydride complex (PCy₃)₂(CO)­RuHCl was found to be a highly effective catalyst for the regio- and stereoselective hydrosilylation of alkynes to form vinylsilane products. (<i>Z</i>)-Vinylsilane products were selectively formed for sterically nondemanding terminal alkynes, while (<i>E</i>)-vinylsilane products resulted from sterically demanding terminal alkynes. Kinetic data were obtained from the hydrosilylation of phenylacetylene. The phosphine inhibition study showed an uncompetitive Michaelis–Menten type of inhibition kinetics. The empirical rate law rate = <i>k</i>_obs[<b>1</b>]¹[alkyne]⁰[silane]⁰ was established from the reaction rate as a function of both [alkyne] and [silane]. DFT calculations were performed and found that <i>Z</i>/<i>E</i> isomerization is facile via a metallacyclopropene transition state and that the isomerization occurs prior to the silane substrate binding. A detailed mechanistic scheme on the hydrosilylation reaction has been delineated on the basis of both experimental and computational data