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The Dehydrogenation of Alcohols through a Concerted Bimetallic Mechanism Involving an Amido-Bridged Diiridium Complex

Authors

  • Dipl.-Chem. Inmaculada Mena,

    1. Instituto de Síntesis Química y Catálisis Homogénea ISQCH, Universidad de Zaragoza-CSIC, C/Pedro Cerbuna, 12, 50009 Zaragoza (Spain)
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  • Dr. Miguel A. Casado,

    Corresponding author
    1. Instituto de Síntesis Química y Catálisis Homogénea ISQCH, Universidad de Zaragoza-CSIC, C/Pedro Cerbuna, 12, 50009 Zaragoza (Spain)
    • Instituto de Síntesis Química y Catálisis Homogénea ISQCH, Universidad de Zaragoza-CSIC, C/Pedro Cerbuna, 12, 50009 Zaragoza (Spain)
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  • Dr. Víctor Polo,

    1. Departamento de Química Física e Instituto de Biocomputación y Física de Sistemas Complejos (BIFI), Universidad de Zaragoza, Zaragoza (Spain)
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  • Dr. Pilar García-Orduña,

    1. Instituto de Síntesis Química y Catálisis Homogénea ISQCH, Universidad de Zaragoza-CSIC, C/Pedro Cerbuna, 12, 50009 Zaragoza (Spain)
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  • Prof. Fernando J. Lahoz,

    1. Instituto de Síntesis Química y Catálisis Homogénea ISQCH, Universidad de Zaragoza-CSIC, C/Pedro Cerbuna, 12, 50009 Zaragoza (Spain)
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  • Prof. Luis A. Oro

    Corresponding author
    1. Instituto de Síntesis Química y Catálisis Homogénea ISQCH, Universidad de Zaragoza-CSIC, C/Pedro Cerbuna, 12, 50009 Zaragoza (Spain)
    • Instituto de Síntesis Química y Catálisis Homogénea ISQCH, Universidad de Zaragoza-CSIC, C/Pedro Cerbuna, 12, 50009 Zaragoza (Spain)
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  • Financial support from the CONSOLIDER INGENIO-2010 program under the projects MULTICAT (CSD2009-00050) and Factoría de Cristalización (CSD2006-0015), and the DGA-ESF are acknowledged. P.G.O. acknowledges financial support from the CSIC “JAE-Doc” program, a contract co-funded by the ESF.

Abstract

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From amido to imido: A dinuclear amido-bridged iridium complex promotes the dehydrogenation of alcohols, affording unusual mixed amido/imido Ir4 and bis(imido) Ir3 clusters. Theoretical calculations suggest that bridging μ-NH2 linkages are crucial to achieve the formation of hydrido amine diiridium species, as a result of a concerted net hydrogen transfer through a proposed eight-membered dimetallacycle.

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