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Updated: Feb 1, 2026

Processing of Bulk Nanocrystalline Metals at the US Army Research Laboratory
Published on: March 7, 2018
Consecutive ligand-based PCET processes affording a doubly reduced nickel pyrazinedithiolate which transforms into a
Keita Koshiba1, Kosei Yamauchi, Ken Sakai
1Department of Chemistry, Faculty of Science, Kyushu University, Motooka 744, Nishi-ku, Fukuoka 819-0395, Japan. kyamauchi@chem.kyushu-univ.jp ksakai@chem.kyushu-univ.jp.
Abstract:
Our DFT results demonstrate that hydrogen evolution from water catalyzed by a nickel pyradinedithiolate (dcpdt) molecular hydrogen evolution catalyst [NiII(dcpdt)2]2- proceeds via the formation of a square-planar nickel(ii) hydride intermediate which is given by unprecedented structural transformation of a doubly reduced triply protonated species [NiII(dcpdtH2)(dcpdtH)]-, afforded as a result of two consecutive ligand-based reductions of [NiII(dcpdt)(dcpdtH)]- through proton-coupled electron transfer (PCET) pathways.
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