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

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

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

7 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)15354-15357
Number of pages4
JournalJournal of the American Chemical Society
Volume137
Issue number49
DOIs
StatePublished - Dec 16 2015

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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