N-heterocyclic carbene complexes of Rh: reaction with dioxygen without oxidation |
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| Authors: | Praetorius Jeremy M Allen Daryl P Wang Ruiyao Webb Jonathan D Grein Friedrich Kennepohl Pierre Crudden Cathleen M |
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| Institution: | Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, Ontario, Canada K7L 3N6. |
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| 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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