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

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dc.authoridGurdal, Yeliz/0000-0002-6245-891X
dc.authoridprobst, benjamin/0000-0001-8850-9685
dc.contributor.authorAlberto, Roger
dc.contributor.authorIannuzzi, Marcella
dc.contributor.authorGurdal, Yeliz
dc.contributor.authorProbst, Benjamin
dc.date.accessioned2025-04-09T09:20:50Z
dc.date.available2025-04-09T09:20:50Z
dc.date.issued2019
dc.description.abstractProton 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.
dc.description.sponsorshipSwiss Science Foundation (Singergia Project) [CRSII2_160801/1]; University of Zurich through University Research Priority Program (URPP) LightChEC; PRACE
dc.description.sponsorshipFor financial support of this work, we are grateful to the Swiss Science Foundation (Singergia Project CRSII2_160801/1) as well as to the University of Zurich through University Research Priority Program (URPP) LightChEC. We acknowledge PRACE for awarding us access to Marconi at CINECA, Italy.
dc.identifier.doi10.2533/chimia.2019.906
dc.identifier.endpage912
dc.identifier.issn0009-4293
dc.identifier.issue11
dc.identifier.pmid31753071
dc.identifier.scopus2-s2.0-85075467046
dc.identifier.scopusqualityQ3
dc.identifier.startpage906
dc.identifier.urihttps://doi.org/10.2533/chimia.2019.906
dc.identifier.urihttps://hdl.handle.net/20.500.14669/3413
dc.identifier.volume73
dc.identifier.wosWOS:000498845300006
dc.identifier.wosqualityQ3
dc.indekslendigikaynakWeb of Science
dc.indekslendigikaynakScopus
dc.indekslendigikaynakPubMed
dc.language.isoen
dc.publisherSwiss Chemical Soc
dc.relation.ispartofChimia
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanı
dc.rightsinfo:eu-repo/semantics/openAccess
dc.snmzKA_20241211
dc.subjectAb initio Molecular dynamics
dc.subjectCobalt polypyridyl
dc.subjectDensity functional theory
dc.subjectPourbaix diagram
dc.subjectProton coupled electron transfer
dc.title[CoII(BPyPy2COH)(OH2)2]2+: A Catalytic Pourbaix Diagram and AIMD Simulations on Four Key Intermediates
dc.typeArticle

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