Pushing Single-Oxygen-Atom-Bridged Bimetallic Systems to the Right: A Cryptand-Encapsulated Co–O–Co Unit
by 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 and Christopher C. Cummins
/
1d
// keep unread
// hide
// preview
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.
http://pubs.acs.org/doi/pdf/10.1021/jacs.5b09827
Visit Website
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.
http://pubs.acs.org/doi/pdf/10.1021/jacs.5b09827
コメント