Alberto, RogerIannuzzi, MarcellaGurdal, YelizProbst, Benjamin2025-04-092025-04-0920190009-429310.2533/chimia.2019.9062-s2.0-85075467046https://doi.org/10.2533/chimia.2019.906https://hdl.handle.net/20.500.14669/3413Proton reduction by [Co-II(BPyPy2COH)(OH2)(2)](2+)(BPyPy2COH = [2,2'-bipyridin]-6-yl-di[pyridin-2-yllmethanol) proceeds through two distinct, pH-dependent pathways involving proton-coupled electron transfer (PCET), reduction and protonation steps. In this account we give an overview of the key mechanistic aspects in aqueous solution from pH 3 to 10, based on electrochemical data, time-resolved spectroscopy and ab initio molecular dynamics simulations of the key catalytic intermediates. In the acidic pH branch, a PCET to give a Co-III hydride is followed by a reduction and a protonation step, to close the catalytic cycle. At elevated pH, a reduction to Co-I is observed, followed by a PCET to a Co-II hydride, and the catalytic cycle is closed by a slow protonation step. In our simulation, both Co-I and Co-II-H feature a strong interaction with the surrounding solvent via hydrogen bonding, which is expected to foster the following catalytic step.eninfo:eu-repo/semantics/openAccessAb initio Molecular dynamicsCobalt polypyridylDensity functional theoryPourbaix diagramProton coupled electron transferArticle9121131753071Q390673WOS:000498845300006Q3