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

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.