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Issue 1, 2008
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Hydrogen production using cobalt-based molecular catalysts containing a proton relay in the second coordination sphere

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Abstract

The cobalt analogue of a highly active nickel electrocatalyst for hydrogen production has been synthesized and characterized as [Co(PPh2NPh2)2(CH3CN)](BF4)2. In the presence of triflic acid in acetonitrile solution, the complex loses one cyclic diphosphine ligand to form [Co(PPh2NPh2)(CH3CN)3](BF4)2, which has been synthesized independently and stucturally characterized. The latter complex serves as an electrocatalyst for hydrogen formation with a turnover frequency of 90 sāˆ’1 and an overpotential of 285 mV using bromoanilinium tetrafluoroborate as the acid. A similar cobalt complex with a related diphosphine ligand that does not contain a pendant base is not catalytically active, confirming an important role for the pendant amine in the catalytic reaction.

Graphical abstract: Hydrogen production using cobalt-based molecular catalysts containing a proton relay in the second coordination sphere

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Publication details

The article was received on 31 Mar 2008, accepted on 19 May 2008 and first published on 11 Jun 2008


Article type: Paper
DOI: 10.1039/B805309J
Citation: Energy Environ. Sci., 2008,1, 167-174
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    Hydrogen production using cobalt-based molecular catalysts containing a proton relay in the second coordination sphere

    G. M. Jacobsen, J. Y. Yang, B. Twamley, A. D. Wilson, R. M. Bullock, M. Rakowski DuBois and D. L. DuBois, Energy Environ. Sci., 2008, 1, 167
    DOI: 10.1039/B805309J

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