title: N-heterocyclic carbene complexes of Rh: reaction with dioxygen without oxidation.
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.
authors.affiliation: Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, Ontario, Canada K7L 3N6.
authors.forename: Jeremy M
authors.initials: JM
authors.lastname: Praetorius
authors.forename: Daryl P
authors.initials: DP
authors.lastname: Allen
authors.forename: Ruiyao
authors.initials: R
authors.lastname: Wang
authors.forename: Jonathan D
authors.initials: JD
authors.lastname: Webb
authors.forename: Friedrich
authors.initials: F
authors.lastname: Grein
authors.forename: Pierre
authors.initials: P
authors.lastname: Kennepohl
authors.forename: Cathleen M
authors.initials: CM
authors.lastname: Crudden
mesh_terms: D006571:Heterocyclic Compounds / Q000737:chemistry*; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*; D013052:Spectrometry, X-Ray Emission / Q000379:methods
chemical_list: D006571:Heterocyclic Compounds; D009942:Organometallic Compounds; C030011:carbene; D012238:Rhodium; D008697:Methane; D010100:Oxygen