Formate oxidation via β-deprotonation in [Ni(PR 2NR'2)2(CH3CN)] 2+ complexes

Candace S. Seu, Aaron Appel, Michael D. Doud, Daniel L DuBois, Clifford P. Kubiak

Research output: Contribution to journalArticle

42 Citations (Scopus)

Abstract

Recent studies from our laboratories have shown that the [Ni(P R2NR'2)2(CH 3CN)]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(CH 3CN)]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.

Original languageEnglish
Pages (from-to)6480-6490
Number of pages11
JournalEnergy and Environmental Science
Volume5
Issue number4
DOIs
Publication statusPublished - 2012

Fingerprint

formic acid
Deprotonation
Proton transfer
Electrocatalysts
Hydrides
ligand
catalyst
Ligands
Hydrogenase
oxidation
Oxidation
Hydrogen
Catalysts
metal
Metals
experiment
Experiments
laboratory
rate

ASJC Scopus subject areas

  • Renewable Energy, Sustainability and the Environment
  • Environmental Chemistry
  • Pollution
  • Nuclear Energy and Engineering

Cite this

Formate oxidation via β-deprotonation in [Ni(PR 2NR'2)2(CH3CN)] 2+ complexes. / Seu, Candace S.; Appel, Aaron; Doud, Michael D.; DuBois, Daniel L; Kubiak, Clifford P.

In: Energy and Environmental Science, Vol. 5, No. 4, 2012, p. 6480-6490.

Research output: Contribution to journalArticle

Seu, Candace S. ; Appel, Aaron ; Doud, Michael D. ; DuBois, Daniel L ; Kubiak, Clifford P. / Formate oxidation via β-deprotonation in [Ni(PR 2NR'2)2(CH3CN)] 2+ complexes. In: Energy and Environmental Science. 2012 ; Vol. 5, No. 4. pp. 6480-6490.
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