Snapshots of dioxygen activation by copper: the structure of a 1:1 Cu/O(2) adduct and its use in syntheses of asymmetric Bis(mu-oxo) complexes.
The X-ray structure of a 1:1 Cu/O(2) adduct revealed side-on (eta(2)) O(2) coordination. Density functional calculations corroborated the structure, indicated a significant contribution of a Cu(III)-(O(2)(2-)) resonance form, and provided insights into the key bonding interactions. Reaction of a 1:1 adduct supported by a slightly different beta-diketiminate ligand with Cu(I) reagents resulted in the formation of novel asymmetric bis(mu-oxo) complexes that were identified by EPR, UV-vis, and Raman spectroscopy, as well as by an X-ray structure in one instance.
Department of Chemistry, Center for Metals in Biocatalysis, Supercomputer Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, MN 55455, USA.
Nermeen W
NW
Aboelella
Elizabeth A
EA
Lewis
Anne M
AM
Reynolds
William W
WW
Brennessel
Christopher J
CJ
Cramer
William B
WB
Tolman
D003300:Copper / Q000737:chemistry* / Q000378:metabolism; D018360:Crystallography, X-Ray; D008024:Ligands; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry* / Q000378:metabolism; D013056:Spectrophotometry, Ultraviolet; D013059:Spectrum Analysis, Raman
D008024:Ligands; D009942:Organometallic Compounds; D003300:Copper; D010100:Oxygen