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Group 5 Imides and Bis(imide)s as Selective Hydrogenation Catalysts

Authors

  • Thomas L. Gianetti,

    1. Department of Chemistry, University of California Berkeley, California 94720-1460, USA
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    • These authors contributed equally to this work.

  • Henry S. La Pierre,

    1. Department of Chemistry, University of California Berkeley, California 94720-1460, USA
    2. Current address: Department of Chemistry and Pharmacy Inorganic Chemistry, University of Erlangen-Nürnberg 91058 Erlangen, Germany
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    • These authors contributed equally to this work.

  • John Arnold

    1. Department of Chemistry, University of California Berkeley, California 94720-1460, USA
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Abstract

In this microreview, we focus on our work on the development of group 5 imido and bis(imido) semihydrogenation catalysts in the context of previous stoichiometric studies on d0 metal–ligand multiple-bond activations of strong σ bonds and both stoichiometric and catalytic studies on H2 activation and hydrogenation by d2 group 5 complexes. These studies develop electronic structure models and mechanistic analyses necessary for the application of catalytic reactions involving 1,2-addition reactions of σ-bonded substrates across early transition metal–ligand multiple bonds. Extension of these studies to the second and third row group 5 imido complexes has led to the development of mechanistically distinct hydrogenation catalysts with product selectivities not readily obtainable with traditional late transition-metal catalysts that employ H2 as the reductant.

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