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

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

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