期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 137, 期 49, 页码 15354-15357出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.5b09827
关键词
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资金
- National Science Foundation [CHE1305124]
- U.S. Department of Energy (DOE) [DE-SC0009565]
- Laboratory Directed Research and Development (LDRD) program at Argonne National Laboratory
- Joseph J. Katz Postdoctoral Fellowship at Argonne National Laboratory (ANL)
- Division of Chemical Sciences, Biosciences, Office of Basic Energy Sciences, DOE [DE-AC02-06CH11357]
- DOE [DE-AC02-06CH11357]
- DOE, Office of Basic Energy Sciences, under SciDAC grant [DE-SC0008666]
- U.S. Department of Energy (DOE) [DE-SC0009565] Funding Source: U.S. Department of Energy (DOE)
A dicobalt(II) complex, [Co-2(mBDCA-5t](2-) (1), demonstrates a cofacial arrangement of trigonal monopyramidal Co(II) ions with an inter-metal separation of 6.2710(6) angstrom. Reaction of 1 with potassium superoxide generates an encapsulated Co-O-Co core in the dianionic complex, [Co2O(mBDCA-5t)](2-) (2); to form the linear Co-O-Co core, the inter-metal distance has diminished to 3.994(3) angstrom. Co K-edge X-ray absorption spectroscopy data are consistent with a +2 oxidation state assignment for Co in both 1 and 2. Multireference complete active space calculations followed by second-order perturbation theory support this assignment, with hole equivalents residing on the bridging O-atom and on the cryptand ligand for the case of 2. Complex 2 acts as a 2-e(-) oxidant toward substrates including CO and H-2, in both cases efficiently regenerating 1 in what represent net oxygen-atom-transfer reactions. This dicobalt system also functions as a catalase upon treatment with H2O2.
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