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Title: Combined Spectroscopic and Electrochemical Detection of a NiI•••H–N Bonding Interaction with Relevance to Electrocatalytic H2 Production

Journal Article · · Chemistry - A European Journal, 21(29):10338-10347
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The [Ni(PR2NR’2)2]2+ family of complexes are exceptionally active catalysts for proton reduction to H2. In this manuscript, we explore the first protonation step of the proposed catalytic cycle by using a catalytically inactive NiI complex possessing a sterically demanding variation of the ligand. Due to the paramagnetic nature of the NiI oxidation state, the protonated NiI intermediate has been characterized through a combination of cyclic voltammetry, ENDOR, and HYSCORE spectroscopy. Both the electrochemical and spectroscopic studies indicate that the NiI complex is protonated at a pendant amine that is endo to Ni, which suggests the presence of an intramolecular NiI•••HN bonding interaction. Using density functional theory, the proton was found to hydrogen bond to three doubly-occupied, localized molecular orbitals: the 3dxz, 3dz2, and 3dyz orbitals of nickel. These studies provide the first direct experimental evidence for this critical catalytic intermediate, and implications for catalytic H2 production are discussed. Research was supported by the Max Planck Society (EPR, ENDOR, and HYSCORE spectroscopy, computational studies), and as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (electrochemistry, NMR spectroscopy). Pacific Northwest National Laboratory is operated by Battelle for DOE.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
DOE Contract Number:
AC05-76RL01830
OSTI ID:
1194278
Report Number(s):
PNNL-SA-108500; KC0307010
Journal Information:
Chemistry - A European Journal, 21(29):10338-10347, Journal Name: Chemistry - A European Journal, 21(29):10338-10347
Country of Publication:
United States
Language:
English

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