Mechanism of olefin hydrosilylation catalyzed by ruCI2(CO)2(PPh3)2

C.T. Tuttle, D. Wang, W. Thiel, J. Weis, J. Kohler, M. Hofmann

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Abstract

Density functional theory (DFT) was used to explore the different mechanistic possibilities for the hydrosilylation reaction between methyldimethoxysilane and methylvinyldimethoxysilane catalyzed by the Ru(II) complex dicarbonyldichlorobis(triphenylphosphine)ruthenium(II) (A1). Reaction enthalpy profiles of the Chalk−Harrod, modified Chalk−Harrod, and σ-bond metathesis mechanisms were computed for several different active forms of A1. A total of 10 different pathways with different catalytic cycles and different induction steps were compared. We predict that a σ-bond metathesis mechanism involving the formation of a hydride analogue of A1 is most favored, in contrast to the commonly accepted Chalk−Harrod mechanism of hydrosilylation. The B3LYP-calculated activation energy within the catalytic cycle (ΔHact = 21.8 kcal/mol) is small enough to make A1 a reasonable catalyst for this reaction under the normally applied experimental conditions
Original languageEnglish
Pages (from-to)4504-4513
Number of pages10
JournalOrganometallics
Volume25
DOIs
Publication statusPublished - 2006

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Keywords

  • density functional theory
  • Chalk−Harrod method
  • hydrosilylations

Cite this

Tuttle, C. T., Wang, D., Thiel, W., Weis, J., Kohler, J., & Hofmann, M. (2006). Mechanism of olefin hydrosilylation catalyzed by ruCI2(CO)2(PPh3)2. Organometallics, 25, 4504-4513. https://doi.org/10.1021/om060359h