PNNL

Abstract

One dimensional variable temperature NMR techniques and two dimensional EXSY experiments provide rate constants for proton exchange processes in [Ni(PCy2NBz2)2]2+, an electrocatalyst for oxidation of H2 (PCy2NBz2 = 1,5-diphenyl-3,7-dibenzyl-1,5-diaza-3,7-diphosphacyclooctane). Computational studies provide insight into the details of the proton movement and energetics of these complexes, which contain pendant amines that function as proton relays. Intramolecular proton exchange processes are observed for two of the three experimentally observable isomers of [Ni(PCy2NBzH2)2]2+, which have two N-H bonds but no Ni-H bonds. For these two isomers, the rate constants range from 103 to 104 s-1, depending on isomer and solvent. Analysis of the exchange as a function of temperature yielded a barrier for proton exchange for both isomers of ?G‡ = 11-12 kcal/mol, with little dependence on solvent. Density functional theory calculations and molecular dynamics simulations support the experimental observations, suggesting a metal-mediated intramolecular proton transfer. Intermolecular proton exchange was not observed on either of these timescales (10-2 s-1 to 104 s-1). The fast rate of proton movement within the catalyst has important implications for the availability of protons during catalysis and may also have implications for the proton channel in the Ni-Fe hydrogenase enzyme. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.