N-heterocyclic carbene complexes of Rh: reaction with dioxygen without oxidation.
|Title||N-heterocyclic carbene complexes of Rh: reaction with dioxygen without oxidation.|
|Publication Type||Journal Article|
|Year of Publication||2008|
|Authors||Praetorius JM, Allen DP, Wang R, Webb JD, Grein F, Kennepohl P, Crudden CM|
|Journal||Journal of the American Chemical Society|
|Date Published||2008 Mar 26|
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.
|Alternate Journal||J. Am. Chem. Soc.|