TY - JOUR
T1 - Pushing Single-Oxygen-Atom-Bridged Bimetallic Systems to the Right
T2 - A Cryptand-Encapsulated Co-O-Co Unit
AU - Stauber, Julia M.
AU - Bloch, Eric D.
AU - Vogiatzis, Konstantinos D.
AU - Zheng, Shao Liang
AU - Hadt, Ryan G.
AU - Hayes, Dugan
AU - Chen, Lin X.
AU - Gagliardi, Laura
AU - Nocera, Daniel G.
AU - Cummins, Christopher C.
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/12/16
Y1 - 2015/12/16
N2 - 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.
AB - 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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U2 - 10.1021/jacs.5b09827
DO - 10.1021/jacs.5b09827
M3 - Article
C2 - 26559923
AN - SCOPUS:84950257643
SN - 0002-7863
VL - 137
SP - 15354
EP - 15357
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 49
ER -