期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 142, 期 28, 页码 12265-12276出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.0c03867
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资金
- Robert A. Welch Foundation [N-190020190330]
- National Institutes of Health (NIH) [R15GM128078]
- NSF [CHE-1454455]
- 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]
Structural, spectroscopic, and reactivity studies are presented for an electron transfer series of copper hydroxide complexes supported by a tridentate redox-active ligand. Single crystal X-ray crystallography shows that the mononuclear [CuOH](1+) core is stabilized via intramolecular H-bonds between the H-donors of the ligand and the hydroxide anion when the ligand is in its trianionic form. This complex undergoes two reversible oxidation processes that produce two metastable high-valent CuOH species, which can be generated by addition of stoichiometric amounts of 1e(-) oxidants. These CuOH species are characterized by an array of spectroscopic techniques including UV-vis absorption, electron paramagnetic resonance (EPR), and X-ray absorption spectroscopies (XAS), which together indicate that all redox couples are ligand-localized. The reactivity of the complexes in their higher oxidation states toward substrates with modest O-H bond dissociation energies (e.g., 4-substitued-2,6-di-tert-butylphenols) indicates that these complexes act as 2H(+)/2e(-) oxidants, differing from the 1H(+)/1e(-) reactivity of well-studied [CuOH](2+) systems.
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