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Issue 4, 2012
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Formate oxidationvia β-deprotonation in [Ni(PR2NR′2)2(CH3CN)]2+ complexes

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Abstract

Recent studies from our laboratories have shown that the [Ni(PR2NR′2)2(CH3CN)]2+ complexes originally developed as artificial hydrogenases are also active electrocatalysts for formate oxidation (TOF ∼16 s−1). The focus of the current work is to develop a detailed understanding of the catalytic mechanism, which would aid in the design of improved catalysts for the interconversion of CO2 and formate. Based on electrochemical and spectroscopic experiments, including data for a new [Ni(PCy2NPhOMe2)2(CH3CN)]2+ complex, we propose a mechanism in which the rate-determining step is a proton transfer from the Ni–O2CH β-H to the ligand pendant base coupled with a 2e transfer to Ni(II), circumventing direct hydride transfer to the metal.

Graphical abstract: Formate oxidation via β-deprotonation in [Ni(PR2NR′2)2(CH3CN)]2+ complexes

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Article information


Submitted
30 Nov 2011
Accepted
17 Jan 2012
First published
16 Feb 2012

Energy Environ. Sci., 2012,5, 6480-6490
Article type
Paper

Formate oxidation via β-deprotonation in [Ni(PR2NR′2)2(CH3CN)]2+ complexes

C. S. Seu, A. M. Appel, M. D. Doud, D. L. DuBois and C. P. Kubiak, Energy Environ. Sci., 2012, 5, 6480
DOI: 10.1039/C2EE03341K

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