This work demonstrates the impact of intramolecular hydrogen bonding (H-bonding) on the calculated pKa of octahedral tris-(pyridinethiolato)nickel (II), [Ni(PyS)3]-, proton reduction catalysts. Density Functional Theory (DFT) calculations on a [Ni(PyS)3]-...

This work demonstrates a strategy to fine-tune the efficiency of a photoredox water splitting Ni(II) tris-pyridinethiolate catalyst through heteroleptic ligand design using computational investigation of the catalytic mechanism. Density functional theory (DFT) calculations, supported by topology analyses using quantum theory of atoms in molecules (QTAIM), show that the introduction of electron donating (ED) −CH 3 and electron withdrawing (EW) −CF 3 groups on the thiopyridyl (PyS − ) ligands of the same complex can tune the pK a and E 0 , simultaneously. Computational modeling of two heteroleptic nickel(II) trispyridinethiolate complexes with 2:1 and 1:2 ED and EW −CH 3 and −CF 3 group containing PyS − ligands, respectively, suggests that the ideal combination of EW to ED groups is 2:1. This work also outlines the possibility of formation of a large number of isomers after the protonation of one of the pyridyl N atoms and suggests that to acquire unambiguous computational results it is necessary to carefully account for all possible geometric isomers.