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Fundamental World of Quantum Chemistry pp 619–643Cite as

Exploring the Catalytic Cycle of the Hydrosilylation of Alkenes Catalyzed by Hydrido-Bridged Diplatinum Complexes Using Electronic Structure Calculation Methods

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Abstract

A comprehensive and consistent picture of the catalytic cycle of hydrosilylation of alkenes catalysed by hydrido-bridged diplatinum complexes has been derived by means of electronic structure calculations at the B3LYP and CCSD(T) levels of theory, using the LANL2DZ basis set. All crucial reaction steps of the entire catalytic course have been scrutinized. Two critical steps of the catalytic cycle corresponding to the hydride migration to the acceptor C atom of the coordinated olefin substrate and the reductive elimination of the hydrosilylated product were found to be the rate-determining steps with activation barriers in the range of 14–20 and 20–31 kcal mol-1, respectively. The role of the hydrosilane, the “spectator” phosphane ligand and the olefin substrate on the catalytic activity and regioselectivity of the hydrosilylation process is also discussed. Finally, the catalyzed hydrosilylation processes are predicted to be exothermic in line with the experimental observations.

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Authors and Affiliations

  1. Laboratory of Applied Quantum Chemistry, Faculty of Chemistry, Aristotle University of Thessaloniki, 541 24, Thessaloniki, Greece

    C. A. Tsipis, A. C. Tsipis & C. E. Kefalidis

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  1. C. A. Tsipis
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  2. A. C. Tsipis
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  3. C. E. Kefalidis
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Editors and Affiliations

  1. Uppsala University, Uppsala, Sweden

    Erkki J. Brändas

  2. Bogoliubov Institute for Theoretical Physics, Kiev, Ukraine

    Eugene S. Kryachko

  3. University of Leuven, Leuven, Belgium

    Eugene S. Kryachko

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Tsipis, C.A., Tsipis, A.C., Kefalidis, C.E. (2004). Exploring the Catalytic Cycle of the Hydrosilylation of Alkenes Catalyzed by Hydrido-Bridged Diplatinum Complexes Using Electronic Structure Calculation Methods. In: Brändas, E.J., Kryachko, E.S. (eds) Fundamental World of Quantum Chemistry. Springer, Dordrecht. https://doi.org/10.1007/978-94-017-0448-9_27

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  • DOI: https://doi.org/10.1007/978-94-017-0448-9_27

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  • Print ISBN: 978-90-481-6687-9

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