Abstract
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. (Z)-Vinylsilane products were selectively formed for sterically nondemanding terminal alkynes, while (E)-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 = kobs[1]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 Z/E 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.
Original language | English (US) |
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Pages (from-to) | 6937-6944 |
Number of pages | 8 |
Journal | Organometallics |
Volume | 33 |
Issue number | 23 |
DOIs | |
State | Published - Dec 8 2014 |
Externally published | Yes |
Bibliographical note
Publisher Copyright:© 2014 American Chemical Society.