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Snapshots of Dioxygen Activation by Copper: The Structure of a 1:1 Cu/O2 Adduct and Its Use in Syntheses of Asymmetric Bis(mu-oxo) Complexes
Aboelella, N. W.; Lewis, E. A.; Reynolds, A. M.; Brennessel, W. W.; Cramer,
C. J.; Tolman, W. B.
J. Am. Chem. Soc.
2002, 124, 10660.
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The X-ray structure of a 1:1 Cu/O2 adduct revealed side-on (eta2) O2 coordination. Density functional calculations corroborated the structure, indicated a significant contribution of a Cu(III)-(O22-) 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.
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