Why do Cationic Hydridoiridium(III) Complexes with β-Aminophosphane Ligands Favour the Transfer Hydrogenation of Ketones over the Direct “H2-Hydrogenation”?—A Computational Approach

Authors

  • Ralph Puchta Dr.,

    1. Computer-Chemie Centrum (CCC), Friedrich-Alexander-Universität Erlangen-Nürnberg, Nägelsbachstr. 25, 91052 Erlangen (Germany), Fax: (+49) 9131-8526565
    2. Institut für Anorganische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 1, 91058 Erlangen (Germany), Fax: (+49) 9131-8527387
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  • Lutz Dahlenburg Prof. Dr.,

    1. Institut für Anorganische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 1, 91058 Erlangen (Germany), Fax: (+49) 9131-8527387
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  • Timothy Clark Prof. Dr.

    1. Computer-Chemie Centrum (CCC), Friedrich-Alexander-Universität Erlangen-Nürnberg, Nägelsbachstr. 25, 91052 Erlangen (Germany), Fax: (+49) 9131-8526565
    2. Interdisciplinary Center for Molecular Materials, Nägelsbachstr. 25, 91052 Erlangen (Germany)
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Abstract

Density functional theory and ab initio molecular orbital calculations show that the observed inability of cationic hydridoiridium(III) complexes with β-aminophosphane ligands to catalyse the direct hydrogenation of carbonyl compounds with dihydrogen (“H2-hydrogenation”) in contrast to their ruthenium(II) equivalents is due to the inability of H2 to displace a coordinated solvent molecule from an intermediate hydrido complex.

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