title: Electrocatalytic Hydrogen Production by a Nickel(II) Complex with a Phosphinopyridyl Ligand.
abstract: A novel nickel(II) complex [Ni(L)2 Cl]Cl with a bidentate phosphinopyridyl ligand 6-((diphenylphosphino)methyl)pyridin-2-amine (L) was synthesized as a metal-complex catalyst for hydrogen production from protons. The ligand can stabilize a low Ni oxidation state and has an amine base as a proton transfer site. The X-ray structure analysis revealed a distorted square-pyramidal Ni(II)  complex with two bidentate L ligands in a trans arrangement in the equatorial plane and a chloride anion at the apex. Electrochemical measurements with the Ni(II) complex in MeCN indicate a higher rate of hydrogen production under weak acid conditions using acetic acid as the proton source. The catalytic current increases with the stepwise addition of protons, and the turnover frequency is 8400 s(-1) in 0.1 m [NBu4 ][ClO4 ]/MeCN in the presence of acetic acid (290 equiv) at an overpotential of circa 590 mV.
authors.affiliation: Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa, Nagoya, 466-8555, Japan.
authors.forename: Ryo
authors.initials: R
authors.lastname: Tatematsu
authors.affiliation: Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa, Nagoya, 466-8555, Japan.
authors.forename: Tomohiko
authors.initials: T
authors.lastname: Inomata
authors.affiliation: Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa, Nagoya, 466-8555, Japan.
authors.forename: Tomohiro
authors.initials: T
authors.lastname: Ozawa
authors.affiliation: Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa, Nagoya, 466-8555, Japan. masuda.hideki@nitech.ac.jp.
authors.forename: Hideki
authors.initials: H
authors.lastname: Masuda
keywords: electrocatalysis; electrochemistry; hydrogen; hydrogenases; nickel