Chemistry Commons^™

Computational Investigation Of The Mechanism Of An Octahedral Ni(Ii) Proton Reduction Catalyst And Importance Of Intramolecular Hydrogen Bonding, Avik Bhattacharjee, Dayalis S.V. Brown, Carolyn N. Virca, Trent E. Ethridge, Oreana Mendez Galue, Uyen T. Pham, Theresa M. Mccormick

Student Research Symposium

Water-splitting to make hydrogen gas is of extreme importance in the field of alternative energy research. Transition-metal complexes are capable of catalyzing the conversion of water to hydrogen at higher pH, with low overpotential. Our research focuses on the importance of intramolecular hydrogen bonding (H-bonding) on the pKa and thermodynamic stability of the catalytic intermediates of a well-known proton-reduction catalyst, nickel (II) tris-pyridinethiolate. Density Functional Theory (DFT) calculations on the parent catalyst and eleven derivatives demonstrate geometric isomer formation after the protonation step of catalysis. These isomers differ in the relative thermodynamic stabilities and pKa values, which can be attributed …