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Catalysis of Proton Reduction by a [BO_4]-Bridged Dicobalt Glyoxime

Laga, Stephanie M. and Blakemore, James D. and Henling, Lawrence M. and Brunschwig, Bruce S. and Gray, Harry B. (2014) Catalysis of Proton Reduction by a [BO_4]-Bridged Dicobalt Glyoxime. Inorganic Chemistry, 53 (24). pp. 12668-12670. ISSN 0020-1669. doi:10.1021/ic501804h.

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We report the preparation of a dicobalt compound with two singly proton-bridged cobaloxime units linked by a central [BO_4] bridge. Reaction of a doubly proton-bridged cobaloxime complex with trimethyl borate afforded the compound in good yield. Single-crystal X-ray diffraction studies confirmed the bridging nature of the [BO_4] moiety. Using electrochemical methods, the dicobalt complex was found to be an electrocatalyst for proton reduction in acetonitrile solution. Notably, the overpotential for proton reduction (954 mV) was found to be higher than in the cases of two analogous single-site cobalt glyoximes under virtually identical conditions.

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Blakemore, James D.0000-0003-4172-7460
Brunschwig, Bruce S.0000-0002-6135-6727
Gray, Harry B.0000-0002-7937-7876
Alternate Title:Catalysis of Proton Reduction by a [BO4]-Bridged Dicobalt Glyoxime
Additional Information:© 2014 American Chemical Society. Received: July 28, 2014; published: November 19, 2014. The authors thank Ivonne Ferrer for helpful discussions and Aaron Sattler for assistance in preparation of Figure 2. This research was carried out in part at the Molecular Materials Research Center of the Beckman Institute at Caltech. The research was supported by the Resnick Sustainability Institute at Caltech (Postdoctoral Fellowship to J.D.B.) and the NSF CCI Solar Fuels Program (CHE-1305124 and a CCI Postdoctoral Fellowship to J.D.B.). The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology (CHE-0639094). Gas chromatographs were collected at the Joint Center for Artificial Photosynthesis at Caltech.
Group:Resnick Sustainability Institute, CCI Solar Fuels, JCAP
Funding AgencyGrant Number
Resnick Sustainability InstituteUNSPECIFIED
NSF Postdoctoral FellowshipUNSPECIFIED
Issue or Number:24
Record Number:CaltechAUTHORS:20141201-105741726
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Official Citation:Catalysis of Proton Reduction by a [BO4]-Bridged Dicobalt Glyoxime Stephanie M. Laga, James D. Blakemore, Lawrence M. Henling, Bruce S. Brunschwig, and Harry B. Gray Inorganic Chemistry 2014 53 (24), 12668-12670
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:52221
Deposited By: Tony Diaz
Deposited On:01 Dec 2014 19:15
Last Modified:10 Nov 2021 19:22

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