"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"

Sergey Koroidov: Kiryong Hong, Kasper S. Kjaer, Lin L, Kristjan Kunnu, Marco Reinhard, Robert W. Hartsock, Das Amit, Richard Eisenberg, C. Das Pemmaraju, Kelly J. Gaffney, Amy A. Cordones; Inorganic Chemistry, 10/11/18.

Additional Authors: Kiryong Hong, Kasper S. Kjaer, Lin L, Kristjan Kunnu, Marco Reinhard, Robert W. Hartsock, Das Amit, Richard Eisenberg, C. Das Pemmaraju, Kelly J. Gaffney, Amy A. Cordones

Abstract:

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 H2 generation.