@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} } @article {ISI:000244896900002, title = {Sulfur K-edge XAS as a probe of sulfur-centered radical intermediates.}, journal = {J. Am. Chem. Soc.}, volume = {129}, number = {11}, year = {2007}, month = {mar}, pages = {3034{\textendash}5}, abstract = {Sulfur K-edge XAS is used in the identification and characterization of sulfur based radicals obtained from UV irradiated glutathione. Ground state and time-dependent DFT calculations are used to identify thiyl (RS center dot) and perthiyl (RSS center dot) radical species.}, keywords = {DFT, Free Radicals, Free Radicals: analysis, Free Radicals: chemistry, GLUTATHIONE, Glutathione: chemistry, Oxidation-Reduction, PHOTOCHEMISTRY, SPECTROMETRY, SPECTROPHOTOMETRY, Sulfhydryl Compounds, Sulfhydryl Compounds: chemistry, SULFUR, sulfur redox, Sulfur: chemistry, ULTRAVIOLET, X-Ray Emission, X-Ray Emission: methods, XAS}, issn = {0002-7863}, doi = {10.1021/ja0676760}, url = {http://www.ncbi.nlm.nih.gov/pubmed/17319664}, author = {Martin-Diaconescu, Vlad and Kennepohl, Pierre} }