Snapshots of a Reversible Metal–Ligand Two-Electron Transfer Step Involving Compounds Related by Multiple Types of Isomerism

Authors

  • Cristina Tejel,

    1. Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Departamento de Química Inorgánica, CSIC – Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza, Spain, Fax: +34-976-761187
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  • Laura Asensio,

    1. Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Departamento de Química Inorgánica, CSIC – Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza, Spain, Fax: +34-976-761187
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  • M. Pilar del Río,

    1. Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Departamento de Química Inorgánica, CSIC – Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza, Spain, Fax: +34-976-761187
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  • Bas de Bruin,

    1. Van 't Hoff Institute for Molecular Sciences, University ofAmsterdam, Science Park 904, 1098 XH, Amsterdam, the Netherlands
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  • José A. López,

    1. Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Departamento de Química Inorgánica, CSIC – Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza, Spain, Fax: +34-976-761187
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  • Miguel A. Ciriano

    1. Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Departamento de Química Inorgánica, CSIC – Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza, Spain, Fax: +34-976-761187
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Abstract

An unusual and very fast equilibrium between two isomers, [(cod)Rh–I{(bpa – 2H)0}IrI(cod)][rlhar2][(cod)RhI{(bpa – 2H)2–}IrI(cod)], which simultaneously display multiple types of isomerism: ligand–metal redox (electromerism), linkage, bond-stretch and ring-slippage isomerism, has been studied by NMR spectroscopy and DFT calculations. Both isomers have been isolated by making rational use of their thermodynamic parameters (ΔH° = +1.93 kcal mol–1; ΔS° = +7.8 cal mol–1 K–1), and have been characterized by X-ray diffraction methods. The equilibrium that involves a two-electron exchange between a redox noninnocent ligand, which transforms from a deprotonated amido form into an imine, and a metal that is reduced, could elucidate a thus far obscure step in the oxidative dehydrogenation of amines to imines.

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