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  • Title: N-heterocyclic carbene complexes of Rh: reaction with dioxygen without oxidation.
    Author: Praetorius JM, Allen DP, Wang R, Webb JD, Grein F, Kennepohl P, Crudden CM.
    Journal: J Am Chem Soc; 2008 Mar 26; 130(12):3724-5. PubMed ID: 18321109.
    Abstract:
    The reaction of oxygen with rhodium complexes containing N-heterocyclic carbenes was found to give dioxygen complexes with rare square planar geometries and unusually short O-O bond lengths. Analysis of the bonding in these complexes by Rh L-edge X-ray absorption spectroscopy (XAS), Raman spectroscopy, and DFT calculations provides evidence for a bonding model in which singlet oxygen is bound to a Rh(I) d8 metal complex, rather than the more common Rh(III) d6 peroxo species with octahedral geometry and O-O bond lengths in the 1.4-1.5 A range.
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