Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 139, Issue 38, Pages 13507-13517Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b07186
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Funding
- NSF [CAREER: CHE-1454455]
- ACS [55181-DNI6]
- DOE [DE-FG02-05ER15690]
- NIH from the NIGMS [T32GM008500]
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-76SF00515]
- Department of Energy's Office of Biological and Environmental Research
- NIH/HIGMS [P41GM103393]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1454455] Funding Source: National Science Foundation
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Copper/aminoxyl species are proposed as key intermediates in aerobic alcohol oxidation. Several possible electronic structural descriptions of these species are possible, and the present study probes this issue by examining four crystallographically characterized Cu/aminoxyl halide complexes by Cu K-edge, Cu L-2,L-3-edge, and Cl K-edge X-ray absorption spectroscopy. The mixing coefficients between Cu, aminoxyl, and halide orbitals are determined via these techniques with support from density functional theory. The emergent electronic structure picture reveals that Cu coordination confers appreciable oxoammonium character to the aminoxyl ligand. The computational methodology is extended to one of the putative intermediates invoked in catalytic Cu/aminoxyl-driven alcohol oxidation reactions, with similar findings. Collectively, the results have important implications for the mechanism of alcohol oxidation and the underlying basis for cooperativity in this co-catalyst system.
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