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

Tuttle, C.T. and Wang, D. and Thiel, W. and Weis, J. and Kohler, J. and Hofmann, M. (2006) Mechanism of olefin hydrosilylation catalyzed by ruCI2(CO)2(PPh3)2. Organometallics, 25. pp. 4504-4513. ISSN 0276-7333

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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

Item type: Article
ID code: 9891
Keywords: density functional theory, Chalk−Harrod method, hydrosilylations, Chemistry, Organic Chemistry, Physical and Theoretical Chemistry, Inorganic Chemistry
Subjects: Science > Chemistry
Department: Faculty of Science > Pure and Applied Chemistry
Unknown Department
Related URLs:
    Depositing user: Strathprints Administrator
    Date Deposited: 25 Nov 2011 11:59
    Last modified: 04 Sep 2014 20:19
    URI: http://strathprints.strath.ac.uk/id/eprint/9891

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