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CO Activation and Reactivity in Organometallic Chemistry: Theoretical Studies

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Quantum Chemistry: The Challenge of Transition Metals and Coordination Chemistry

Part of the book series: NATO ASI Series ((ASIC,volume 176))

Abstract

SCF and CI calculations are reported for two elementary-reactions involved in CO reductive hydrogenation catalytic processes, the nucleophilic addition of a hydride to the carbonyl ligand and the carbonyl insertion into the metal hydride bond. The nucleophilic addition is found to be exothermic and with no activation barrier. The CO insertion reaction is shown to be an hydride migration toward the carbonyl ligand and is characterized by a high energy barrier. The factors which control the corresponding stereochemistries and energy profiles are analyzed in connection with experimental gas phase and solution data. The importance of correlation effects is also discussed.

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Authors and Affiliations

  1. Laboratoire de Chimie Quantique E.R. n° 139 du CNRS, Université Louis Pasteur, 4, rue B. Pascal, F-67000, Strasbourg, France

    A. Dedieu & S. Nakamura

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  1. A. Dedieu
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  2. S. Nakamura
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  1. Centre National de la Recherche Scientifique, Strasbourg, France

    A. Veillard

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© 1986 D. Reidel Publishing Company

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Dedieu, A., Nakamura, S. (1986). CO Activation and Reactivity in Organometallic Chemistry: Theoretical Studies. In: Veillard, A. (eds) Quantum Chemistry: The Challenge of Transition Metals and Coordination Chemistry. NATO ASI Series, vol 176. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-4656-9_20

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  • DOI: https://doi.org/10.1007/978-94-009-4656-9_20

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-90-277-2237-9

  • Online ISBN: 978-94-009-4656-9

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