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Stauber JM, Bloch ED, Vogiatzis KD, et al. Pushing Single-Oxygen-Atom-Bridged Bimetallic Systems to the Right: A Cryptand-Encapsulated Co-O-Co Unit. J Am Chem Soc. 2015;137(49):15354-7doi: 10.1021/jacs.5b09827.
Stauber, J. M., Bloch, E. D., Vogiatzis, K. D., Zheng, S. L., Hadt, R. G., Hayes, D., Chen, L. X., Gagliardi, L., Nocera, D. G., & Cummins, C. C. (2015). Pushing Single-Oxygen-Atom-Bridged Bimetallic Systems to the Right: A Cryptand-Encapsulated Co-O-Co Unit. Journal of the American Chemical Society, 137(49), 15354-7. https://doi.org/10.1021/jacs.5b09827
Stauber, Julia M, et al. "Pushing Single-Oxygen-Atom-Bridged Bimetallic Systems to the Right: A Cryptand-Encapsulated Co-O-Co Unit." Journal of the American Chemical Society vol. 137,49 (2015): 15354-7. doi: https://doi.org/10.1021/jacs.5b09827
Stauber JM, Bloch ED, Vogiatzis KD, Zheng SL, Hadt RG, Hayes D, Chen LX, Gagliardi L, Nocera DG, Cummins CC. Pushing Single-Oxygen-Atom-Bridged Bimetallic Systems to the Right: A Cryptand-Encapsulated Co-O-Co Unit. J Am Chem Soc. 2015 Dec 16;137(49):15354-7. doi: 10.1021/jacs.5b09827. Epub 2015 Dec 07. PMID: 26559923.
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J Am Chem Soc. 2015 Dec 16;137(49):15354-7. doi: 10.1021/jacs.5b09827. Epub 2015 Dec 07.

Pushing Single-Oxygen-Atom-Bridged Bimetallic Systems to the Right: A Cryptand-Encapsulated Co-O-Co Unit.

Journal of the American Chemical Society

Julia M Stauber, Eric D Bloch, Konstantinos D Vogiatzis, Shao-Liang Zheng, Ryan G Hadt, Dugan Hayes, Lin X Chen, Laura Gagliardi, Daniel G Nocera, Christopher C Cummins

Affiliations

  1. Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
  2. Department of Chemistry and Chemical Biology, Harvard University , Cambridge, Massachusetts 02138, United States.
  3. Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota , Minneapolis, Minnesota 55455, United States.
  4. Chemical Sciences and Engineering Division, Argonne National Laboratory , Lemont, Illinois 60439, United States.

PMID: 26559923 DOI: 10.1021/jacs.5b09827

Abstract

A dicobalt(II) complex, [Co2(mBDCA-5t)](2-) (1), demonstrates a cofacial arrangement of trigonal monopyramidal Co(II) ions with an inter-metal separation of 6.2710(6) Å. 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) Å. 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 H2, 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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