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Enantioselective Hydrosilylation by Chiral Pd Based Homogeneous Catalysts with First-Principles and Combined QM/MM Molecular Dynamics Simulations

  • Chapter
Computational Modeling of Homogeneous Catalysis

Part of the book series: Catalysis by Metal Complexes ((CMCO,volume 25))

Abstract

The enantioselective hydrosilylation of styrene catalyzed by Pd0 species generated in situ from dichloro{1-{(R)-1-[(S) 2 (diphenylphosphino- κP) ferrocenyl]ethyl}-3-trimethylphenyl-5-1H-pyrazole-κN} palladium. 1, has been investigated in detail by ab initio molecular dynamics and combined quantum mechanics and molecular mechanics (QM/MM) simulations. The nature of the unique structural features observed in the pre-catalyst, 1, and its bis(trichlorosilyl) derivatives have been explored. Using the combined QM/MMmethod we have been able to pinpoint the steric and electronic influence of specific ligands on these geometric distortions. The whole catalytic cycle of the enantioselective styrene hydrosilylation has been examined in detail with mixed QM/MM Car-Parrinello molecular dynamics simulations. The simulations show that the reaction proceeds through the classical Chalk-Harrod mechanism of hydrosilylation. The rate-determining step was found to be the migration of the silyl ligand to the α-carbon of the substrate. The nature of the regiospecificity and enantioselectivity of the catalysis has been established. In both cases the formation of a η3-benzyllic intermediate plays a crucial role. The mechanistic detail afforded by the computational study provides a framework for rationalligand design that would improve the enantioselectivity of the catalysis.

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Author information

Authors and Affiliations

  1. Laboratory of Inorganic Chemistry, Swiss Federal Institute of Technology, ETH Zentrum, CH-8092, Zürich, Switzerland

    Alessandra Magistrato, Antonio Togni & Ursula Röthlisberger

  2. Department of Chemistry, The University of Western Ontario, London, Ontario, Canada, N6A 5B7

    Tom K. Woo

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  1. Alessandra Magistrato
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  2. Antonio Togni
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  3. Ursula Röthlisberger
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  4. Tom K. Woo
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Editors and Affiliations

  1. Unitat de Química Física, Universitat Autònoma de Barcelona, Bellaterra, Catalonia, Spain

    Feliu Maseras  & Agustí Lledós  & 

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Magistrato, A., Togni, A., Röthlisberger, U., Woo, T.K. (2002). Enantioselective Hydrosilylation by Chiral Pd Based Homogeneous Catalysts with First-Principles and Combined QM/MM Molecular Dynamics Simulations. In: Maseras, F., Lledós, A. (eds) Computational Modeling of Homogeneous Catalysis. Catalysis by Metal Complexes, vol 25. Springer, Boston, MA. https://doi.org/10.1007/0-306-47718-1_9

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  • DOI: https://doi.org/10.1007/0-306-47718-1_9

  • Publisher Name: Springer, Boston, MA

  • Print ISBN: 978-1-4020-0933-4

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