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    Oxygen Reduction Reactions of Monometallic Rhodium Hydride Complexes
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    Department of Chemistry, 6-335, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139-4307, United States
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2012, 51, 13, 7192–7201
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    https://doi.org/10.1021/ic300279z
    Published June 18, 2012
    Copyright © 2012 American Chemical Society
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    Abstract

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    Selective reduction of oxygen is mediated by a series of monometallic rhodium(III) hydride complexes. Oxidative addition of HCl to trans-RhICl(L)(PEt3)2 (1a, L = CO; 1b, L = 2,6-dimethylphenylisocyanide (CNXy); 1c, L = 1-adamantylisocyanide (CNAd)) produces the corresponding RhIII hydride complex cis-trans-RhIIICl2H(L)(PEt3)2 (2a–c). The measured equilibrium constants for the HCl-addition reactions show a pronounced dependence on the identity of the “L” ligand. The hydride complexes effect the reduction of O2 to water in the presence of HCl, generating trans-RhIIICl3(L)(PEt3)2 (3a–c) as the metal-containing product. In the case of 2a, smooth conversion to 3a proceeds without spectroscopic evidence for an intermediate species. For 2b/c, an aqua intermediate, cis-trans-[RhIII(OH2)Cl2(L)(PEt3)2]Cl (5b/c), forms along the pathway to producing 3b/c as the final products. The aqua complexes were independently prepared by treating peroxo complexes trans-RhIIICl(L)(η2-O2)(PEt3)2 (4b/c) with HCl to rapidly produce a mixture of 5b/c and 3b/c. The reactivity of the peroxo species demonstrates that they are plausible intermediates in the O2-reduction chemistry of hydride complexes 2a–c. These results together show that monometallic rhodium hydride complexes are capable of promoting selective reduction of oxygen to water and that this reaction may be controlled with systematic alteration of the ancillary ligand set.

    Copyright © 2012 American Chemical Society

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    Supporting Information

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    31P{1H} NMR spectra for aerobic conversion of 2b/c and HCl to 3b/c, electronic spectra for complexes 1a–c, 2b/c, 3a–c, and 4b/c, partial IR spectra for 1b/c–4b/c, and crystallographic information file (CIF). This material is available free of charge via the Internet at http://pubs.acs.org.

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    This article is cited by 22 publications.

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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2012, 51, 13, 7192–7201
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ic300279z
    Published June 18, 2012
    Copyright © 2012 American Chemical Society
    Request reuse permissions

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