N-heterocyclic carbene complexes of Rh: reaction with dioxygen without oxidation.
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.
Praetorius
Jeremy M
JM
Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, Ontario, Canada K7L 3N6.
Allen
Daryl P
DP
Wang
Ruiyao
R
Webb
Jonathan D
JD
Grein
Friedrich
F
Kennepohl
Pierre
P
Crudden
Cathleen M
CM
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
D006571:Heterocyclic Compounds; D009942:Organometallic Compounds; C030011:carbene; D012238:Rhodium; D008697:Methane; D010100:Oxygen