N-heterocyclic carbene complexes of Rh: reaction with dioxygen without oxidation. Praetorius, M, J., Allen, P, D., Wang, R., Webb, D, J., Grein, F., Kennepohl, P., Crudden, & M, C. J. Am. Chem. Soc., 130(12):3724--5, March, 2008. Paper doi abstract bibtex 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.
@article{ ISI:000254173600010,
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.},
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},
doi = {10.1021/ja7108213},
file = {:C$\backslash$:/Users/pierre/My References/J. Am. Chem. Soc/Praetorius et al. - 2008 - N-heterocyclic carbene complexes of Rh reaction with dioxygen without oxidation.pdf:pdf},
issn = {1520-5126},
journal = {J. Am. Chem. Soc.},
keywords = {Chemical,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},
month = {March},
number = {12},
pages = {3724--5},
pmid = {18321109},
title = {{N-heterocyclic carbene complexes of Rh: reaction with dioxygen without oxidation.}},
url = {http://www.ncbi.nlm.nih.gov/pubmed/18321109},
volume = {130},
year = {2008}
}
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