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 |
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| Authors: | Aboelella Nermeen W Lewis Elizabeth A Reynolds Anne M Brennessel William W Cramer Christopher J Tolman William B |
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| Affiliation: | Department of Chemistry, Center for Metals in Biocatalysis, Supercomputer Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, MN 55455, USA. |
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| Abstract: | 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. |
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