期刊
INORGANIC CHEMISTRY
卷 54, 期 18, 页码 9223-9228出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.5b01777
关键词
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资金
- Japan Science and Technology Agency (JST)
- Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan [26620154, 26288037]
- NRF/MEST of Korea [R31-2008-000-10010-0, 2010-00353]
- National Science Foundation [CHE-1463900]
- Grants-in-Aid for Scientific Research [26620154] Funding Source: KAKEN
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1463900] Funding Source: National Science Foundation
Rate constants of electron self-exchange of high-valent oxo and imido complexes of chromium(V/IV) corrole have been determined in acetonitrile and toluene at various temperatures by electron paramagnetic resonance (EPR) line width variation of the EPR spectra. The observed activation enthalpies (Delta H-obs double dagger) of electron self-exchange of chromium(V)-oxo and -imido corrole with the corresponding chromium(IV) complexes are zero in toluene, whereas the Delta H-obs double dagger values are slightly positive in acetonitrile. Such activationless electron self-exchange transfer resulted in extremely fast electron-transfer reactions of chromium(V)-oxo and -imido corrole in sharp contrast with slow electron-transfer reactions of other high-valent metal-oxo and -imido complexes.
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