Dissociation of Pyridinethiolate Ligands during Hydrogen Evolution Reactions of Ni-Based Catalysts: Evidence from X-ray Absorption Spectroscopy.

ABSTRACT: The protonation of several Ni-centered pyridine-2-thiolate photocatalysts for hydrogen evolution is investigated using X-ray absorption spectroscopy (XAS). While protonation of the pyridinethiolate ligand was previously thought to result in partial dechelation from the metal at the pyridyl N site, we instead observe complete dissociation of the protonated ligand and replacement by solvent molecules. A combination of Ni K-edge and S K-edge XAS of the catalyst Ni(bpy)(pyS)₂ (bpy = 2,2'-bipyridine; pyS = pyridine-2-thiolate) identifies the structure of the fully protonated catalyst as a solvated [Ni(bpy)(DMF)₄]²⁺ (DMF = dimethylformamide) complex and the dissociated ligands as the N-protonated 2-thiopyridone (pyS-H). This surprising result is further supported

SUBMITTER: Ledbetter K 

PROVIDER: S-EPMC9257748 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature