Hydrogen production using cobalt-based molecular catalysts containing a proton relay in the second coordination sphere
- 11 June 2008
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Energy & Environmental Science
- Vol. 1 (1), 167-174
- https://doi.org/10.1039/b805309j
Abstract
The cobalt analogue of a highly active nickel electrocatalyst for hydrogen production has been synthesized and characterized as [Co(PPh 2NPh 2)2(CH3CN)](BF4)2. In the presence of triflic acid in acetonitrile solution, the complex loses one cyclic diphosphine ligand to form [Co(PPh 2NPh 2)(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 s−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.Keywords
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