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Electronic Effects on a Mononuclear Co Complex with a Pentadentate Ligand for Catalytic H2 Evolution

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journal contribution
posted on 06.10.2014, 00:00 by Manohar Vennampalli, Guangchao Liang, Lakshmi Katta, Charles Edwin Webster, Xuan Zhao
Previous studies of Co catalysts for H2 evolution have shown opposite effects between the redox potentials of Co centers and their catalytic properties such as the overpotential and turnover frequency: Co catalysts with more positive reduction potentials from structural modification display insignificant changes in the overpotential for H2 evolution and require stronger acid for catalysis, and Co catalysts with lower overpotentials show decreased turnover frequency for H2 evolution. In order to explore the electronic effects of a ligand scaffold on the catalytic properties for H2 evolution by a Co complex with a pentadentate ligand, N,N-bis­(2-pyridinylmethyl)-2,2′-bipyridine-6-methanamine (DPA-Bpy), we replaced the pyridyls in DPA-Bpy with more basic isoquinoline groups. In contrast to data from previously reported studies, in the current study, a Co complex with a more positive reduction potential, resulting from the replacement of pyridyls with isoquinoline groups, leads to a lower overpotential and higher turnover frequency for both electro- and photocatalytic H2 production in neutral aqueous solution.