Computational investigation into intramolecular hydrogen bonding controlling the isomer formation and p of octahedral nickel(II) proton reduction catalysts.

This work demonstrates the impact of intramolecular hydrogen bonding (H-bonding) on the calculated p of octahedral tris-(pyridinethiolato)nickel(II), [Ni(PyS)3]-, proton reduction catalysts. Density Functional Theory (DFT) calculations on a [Ni(PyS)3]- catalyst, and eleven derivatives, demonstrate geometric isomer formation in the protonation step of the catalytic cycle. Through Quantum Theory of Atoms in Molecules (QTAIM), we show that the p of each isomer is driven by intramolecular H-bonding of the proton on the pyridyl nitrogen to a sulfur on a neighboring ligand.