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[CoII(BPyPy2COH)(OH2)2]2+: A Catalytic Pourbaix Diagram and AIMD Simulations on Four Key Intermediates

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Proton reduction by [CoII(BPyPy2COH)(OH2)2]2+ (BPyPy2COH = [2,2'-bipyridin]-6-yl-di[pyridin-2-yl]methanol) 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 CoIII hydride is followed by a reduction and a protonation step, to close the catalytic cycle. At elevated pH, a reduction to CoI is observed, followed by a PCET to a CoII hydride, and the catalytic cycle is closed by a slow protonation step. In our simulation, both CoI and CoII–H feature a strong interaction with the surrounding solvent via hydrogen bonding, which is expected to foster the following catalytic step.
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Keywords: AB INITIO MOLECULAR DYNAMICS; COBALT POLYPYRIDYL; DENSITY FUNCTIONAL THEORY; POURBAIX DIAGRAM; PROTON COUPLED ELECTRON TRANSFER

Document Type: Research Article

Affiliations: 1: Department of Chemistry, University of Zurich, Winterthurerstrasse 190, CH-8057 Zurich 2: Department of Bioengineering, Adana Alparslan Turkes Science and Technology University, Catalan Caddesi 201, Saricam, Adana, Turkey;, Email: [email protected] 3: Department of Chemistry, University of Zurich, Winterthurerstrasse 190, CH-8057 Zurich;, Email: [email protected]

Publication date: November 1, 2019

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  • International Journal for Chemistry and Official Membership Journal of the Swiss Chemical Society (SCS) and its Divisions

    CHIMIA, a scientific journal for chemistry in the broadest sense, is published 10 times a year and covers the interests of a wide and diverse readership. Contributions from all fields of chemistry and related areas are considered for publication in the form of Review Articles and Notes. A characteristic feature of CHIMIA are the thematic issues, each devoted to an area of great current significance.

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