期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 140, 期 5, 页码 1834-1841出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b11953
关键词
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资金
- European Union [FP7-333948, ERC-2015-STG-678202]
- Science Foundation Ireland [SFI/12/RC/2278, SFI/15/RS-URF/3307]
- DOE Office of Science [DE-AC02-76SF00515, DE-SC0012704]
- NIH [P30-EB-009998]
- COST Action [CM1305]
Oxo-metal-halide moieties have often been implicated as C-H bond activating oxidants with the terminal oxo-metal entity identified as the electrophilic oxidant. The electrophilic reactivity of metal-halide species has not been investigated. We have prepared a high-valent nickel-halide complex [Ni-III(Cl)(L)] (2, L = N,N'-(2,6-dimethylphenyl)-2,6-pyridinedicarboxamide) by one-electron oxidation of a [Ni-II(Cl)(L)](-) precursor. 2 was characterized using electronic absorption, electron paramagnetic resonance, and X-ray absorption spectroscopies and mass spectrometry. 2 reacted readily with substrates containing either phenolic O-H or hydrocarbon C-H bonds. Analysis of the Hammett, Evans-Polanyi, and Marcus relationships between the determined rate constants and substrate pK(a), X-H bond dissociation energy, and oxidation potential, respectively, was performed. Through this analysis, we found that 2 reacted by a hydrogen atom transfer (HAT) mechanism. Our findings shine light on enzymatic high-valent oxo-metal-halide oxidants and open new avenues for oxidative halogenation catalyst design.
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