@article {ISI:000254173600010, title = {N-heterocyclic carbene complexes of Rh: reaction with dioxygen without oxidation.}, journal = {J. Am. Chem. Soc.}, volume = {130}, number = {12}, year = {2008}, month = {mar}, pages = {3724{\textendash}5}, 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.}, keywords = {chemical, DFT, dioxygen complexes, Heterocyclic Compounds, Heterocyclic Compounds: chemistry, METHANE, Methane: analogs \& derivatives, Methane: chemistry, models, MOLECULAR, molecular structure, ORGANOMETALLIC COMPOUNDS, Organometallic Compounds: chemical synthesis, Organometallic Compounds: chemistry, OXYGEN, Oxygen: chemistry, rhodium, Rhodium: chemistry, SPECTROMETRY, X-Ray Emission, X-Ray Emission: methods, XAS}, issn = {1520-5126}, doi = {10.1021/ja7108213}, url = {http://www.ncbi.nlm.nih.gov/pubmed/18321109}, author = {Praetorius, Jeremy M and Allen, Daryl P and Wang, Ruiyao and Webb, Jonathan D and Grein, Friedrich and Kennepohl, Pierre and Crudden, Cathleen M} }