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Electrocatalytic Hydrogen Production by a Nickel(II) Complex with a Phosphinopyridyl Ligand
Author(s) -
Tatematsu Ryo,
Inomata Tomohiko,
Ozawa Tomohiro,
Masuda Hideki
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201511621
Subject(s) - overpotential , chemistry , ligand (biochemistry) , nickel , catalysis , denticity , acetic acid , electrochemistry , inorganic chemistry , amine gas treating , medicinal chemistry , metal , organic chemistry , electrode , biochemistry , receptor
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 [NBu 4 ][ClO 4 ]/MeCN in the presence of acetic acid (290 equiv) at an overpotential of circa 590 mV.