High catalytic rates for hydrogen production using nickel electrocatalysts with seven-membered cyclic diphosphine ligands containing one pendant amine

Michael P. Stewart, Ming Hsun Ho, Stefan Wiese, Mary Lou Lindstrom, Colleen E. Thogerson, Simone Raugei, R Morris Bullock, Monte Helm

Research output: Contribution to journalArticle

88 Citations (Scopus)

Abstract

A series of Ni-based electrocatalysts, [Ni(7PPh 2NC6H4X)2](BF4)2, featuring seven-membered cyclic diphosphine ligands incorporating a single amine base, 1-para-X-phenyl-3,6-triphenyl-1-aza-3,6-diphosphacycloheptane (7P Ph 2NC6H4X, where X = OMe, Me, Br, Cl, or CF3), have been synthesized and characterized. X-ray diffraction studies have established that the [Ni(7PPh 2N C6H4X)2]2+ complexes have a square planar geometry, with bonds to four phosphorus atoms of the two bidentate diphosphine ligands. Each of the complexes is an efficient electrocatalyst for hydrogen production at the potential of the Ni(II/I) couple, with turnover frequencies ranging from 2400 to 27 000 s-1 with [(DMF)H]+ in acetonitrile. Addition of water (up to 1.0 M) accelerates the catalysis, giving turnover frequencies ranging from 4100 to 96 000 s-1. Computational studies carried out on the [Ni(7PPh 2NC6H4X) 2]2+ family indicate the catalytic rates reach a maximum when the electron-donating character of X results in the pKa of the Ni(I) protonated pendant amine matching that of the acid used for proton delivery. Additionally, the fast catalytic rates for hydrogen production by the [Ni(7PPh 2NC6H4X)2]2+ family relative to the analogous [Ni(PPh 2N C6H4X 2)2]2+ family are attributed to preferred formation of endo protonated isomers with respect to the metal center in the former, which is essential to attain suitable proximity to the reduced metal center to generate H2. The results of this work highlight the importance of precise pKa matching with the acid for proton delivery to obtain optimal rates of catalysis.

Original languageEnglish
Pages (from-to)6033-6046
Number of pages14
JournalJournal of the American Chemical Society
Volume135
Issue number16
DOIs
Publication statusPublished - Apr 24 2013

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Electrocatalysts
Hydrogen production
Nickel
Catalysis
Amines
Protons
Hydrogen
Metals
Ligands
Acids
Acetonitrile
X-Ray Diffraction
Isomers
Phosphorus
Electrons
X ray diffraction
Atoms
Geometry
Water
acetonitrile

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

High catalytic rates for hydrogen production using nickel electrocatalysts with seven-membered cyclic diphosphine ligands containing one pendant amine. / Stewart, Michael P.; Ho, Ming Hsun; Wiese, Stefan; Lindstrom, Mary Lou; Thogerson, Colleen E.; Raugei, Simone; Bullock, R Morris; Helm, Monte.

In: Journal of the American Chemical Society, Vol. 135, No. 16, 24.04.2013, p. 6033-6046.

Research output: Contribution to journalArticle

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abstract = "A series of Ni-based electrocatalysts, [Ni(7PPh 2NC6H4X)2](BF4)2, featuring seven-membered cyclic diphosphine ligands incorporating a single amine base, 1-para-X-phenyl-3,6-triphenyl-1-aza-3,6-diphosphacycloheptane (7P Ph 2NC6H4X, where X = OMe, Me, Br, Cl, or CF3), have been synthesized and characterized. X-ray diffraction studies have established that the [Ni(7PPh 2N C6H4X)2]2+ complexes have a square planar geometry, with bonds to four phosphorus atoms of the two bidentate diphosphine ligands. Each of the complexes is an efficient electrocatalyst for hydrogen production at the potential of the Ni(II/I) couple, with turnover frequencies ranging from 2400 to 27 000 s-1 with [(DMF)H]+ in acetonitrile. Addition of water (up to 1.0 M) accelerates the catalysis, giving turnover frequencies ranging from 4100 to 96 000 s-1. Computational studies carried out on the [Ni(7PPh 2NC6H4X) 2]2+ family indicate the catalytic rates reach a maximum when the electron-donating character of X results in the pKa of the Ni(I) protonated pendant amine matching that of the acid used for proton delivery. Additionally, the fast catalytic rates for hydrogen production by the [Ni(7PPh 2NC6H4X)2]2+ family relative to the analogous [Ni(PPh 2N C6H4X 2)2]2+ family are attributed to preferred formation of endo protonated isomers with respect to the metal center in the former, which is essential to attain suitable proximity to the reduced metal center to generate H2. The results of this work highlight the importance of precise pKa matching with the acid for proton delivery to obtain optimal rates of catalysis.",
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AU - Lindstrom, Mary Lou

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AU - Bullock, R Morris

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