4.8 Article Retracted Publication

被撤回的出版物: Pushing Single-Oxygen-Atom-Bridged Bimetallic Systems to the Right: A Cryptand-Encapsulated Co-O-Co Unit (Retracted article. See vol. 142, pg. 6834, 2020)

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 137, Issue 49, Pages 15354-15357

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jacs.5b09827

Keywords

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Funding

  1. National Science Foundation [CHE1305124]
  2. U.S. Department of Energy (DOE) [DE-SC0009565]
  3. Laboratory Directed Research and Development (LDRD) program at Argonne National Laboratory
  4. Joseph J. Katz Postdoctoral Fellowship at Argonne National Laboratory (ANL)
  5. Division of Chemical Sciences, Biosciences, Office of Basic Energy Sciences, DOE [DE-AC02-06CH11357]
  6. DOE [DE-AC02-06CH11357]
  7. DOE, Office of Basic Energy Sciences, under SciDAC grant [DE-SC0008666]
  8. U.S. Department of Energy (DOE) [DE-SC0009565] Funding Source: U.S. Department of Energy (DOE)

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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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