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Probing the Electron Accepting Orbitals of Ni-Centered Hydrogen Evolution Catalysts with Noninnocent Ligands by Ni L-Edge and S K-Edge X-ray Absorption
Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA;Stockholm Univ, Dept Phys, AlbaNova Univ Ctr, S-10691 Stockholm, Sweden.
Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA;Korea Res Inst Stand & Sci, Ctr Gas Anal, Div Chem & Med Metrol, Daejeon 34113, South Korea.ORCID iD: 0000-0002-3590-3635
Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA;Lund Univ, Dept Chem Phys, POB 124, S-22100 Lund, Sweden.
Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA.ORCID iD: 0000-0001-6360-2197
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2018 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 57, no 21, p. 13167-13175Article in journal (Refereed) Published
Abstract [en]

The valence electronic structure of several square planar Ni-centered complexes, previously shown to catalyze the hydrogen evolution reaction, are characterized using S K-edge and Ni L-edge X-ray absorption spectroscopy and electronic structure calculations. Measurement of the atomic Ni 3d and S 3p contributions enables assessment of the metal-ligand covalency of the electron accepting valence orbitals and yields insight into the ligand-dependent reaction mechanisms proposed for the catalysts. The electron accepting orbital of the Ni(abt)(2) (abt = 2-aminobenzenethiolate) catalyst is found to have large ligand character (80%), with only 9% S 3p (per S) character, indicating delocalization over the entire abt ligand. Upon two proton-coupled reductions to form the Ni(abt-H)(2) intermediate, the catalyst stores 1.8 electrons on the abt ligand, and the ligand N atoms are protonated, thus supporting its role as an electron and proton reservoir. The electron accepting orbitals of the Ni(abt-H)(2) intermediate and Ni(mpo)(2) (mpo = 2-mercaptopyridyl-N-oxide) catalyst are found to have considerably larger Ni 3d (46-47%) and S 3p (17-18% per S) character, consistent with an orbital localized on the metal-ligand bonds. This finding supports the possibility of metal-based chemistry, resulting in Ni-H bond formation for the reduced Ni(abt-H)(2) intermediate and Ni(mpo)(2) catalyst, a critical reaction intermediate in H-2 generation.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC , 2018. Vol. 57, no 21, p. 13167-13175
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-387252DOI: 10.1021/acs.inorgchem.8b01497ISI: 000449576900016PubMedID: 30351073OAI: oai:DiVA.org:uu-387252DiVA, id: diva2:1332142
Funder
Knut and Alice Wallenberg Foundation, KAW 2014.0370Available from: 2019-06-27 Created: 2019-06-27 Last updated: 2019-06-27Bibliographically approved

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