| 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 | J. Am. Chem. Soc. |
| Volume | 130 |
| Pagination | 3724–5 |
| Date Published | mar |
| ISSN | 1520-5126 |
| 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 |
| 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. |
| URL | http://www.ncbi.nlm.nih.gov/pubmed/18321109 |
| DOI | 10.1021/ja7108213 |
