期刊
INORGANIC CHEMISTRY
卷 53, 期 19, 页码 10195-10202出版社
AMER CHEMICAL SOC
DOI: 10.1021/ic501181k
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资金
- Ministry of Education, Culture, Sports, Science, Cooperative Research in Joint Studies Programs at the Institute for Molecular Science, and Technology of Japan [22550055, 25410060, 25109540]
- Cooperative Research Program of Network Joint Research Center for Materials and Devices (Institute for Materials Chemistry and Engineering, Kyushu University)
- NSERC
- European Union
- State of Hungary
- European Social Fund [TAMOP 4.2.4.A/2-11-1-2012-0001]
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-76SF00515]
- Grants-in-Aid for Scientific Research [25107526, 26104532, 25410060, 24655135, 25109540, 26620160, 25708011] Funding Source: KAKEN
One-electron-oxidized Ni-III-phenoxide complexes with salen-type ligands, [Ni(salen)py(2)](2+) ([1(en)-py](2+)) and [Ni(1,2-salcn)py(2)](2+) ([1(cn)-py](2+)), with a five-membered chelate dinitrogen backbone and [Ni(salpn)py(2)](2+) ([2(pn)-py](2+)) with a six-membered chelate backbone, have been characterized with a combination of experimental and theoretical methods. The five-membered chelate complexes [1(en)-py](2+) and [1(cn)-py](2+) were assigned as Ni-III-phenoxyl radical species, while the six-membered chelate complex [2(pn)-py](2+) was concluded to be a Ni-II-bis(phenoxyl radical) species with metal-centered reduction in the course of the one-electron oxidation of the Ni-III-phenoxide complex [2(pn)-py](+). Thus, the oxidation state of the one-electron-oxidized Ni-III salen-type complexes depends on the chelate ring size of the dinitrogen backbone.
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