[CoII(BPyPy2COH)(OH2)2]2+: A Catalytic Pourbaix Diagram and AIMD Simulations on Four Key Intermediates
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Tarih
2019
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
Swiss Chemical Soc
Erişim Hakkı
info:eu-repo/semantics/openAccess
Özet
Proton 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.
Açıklama
Anahtar Kelimeler
Ab initio Molecular dynamics, Cobalt polypyridyl, Density functional theory, Pourbaix diagram, Proton coupled electron transfer
Kaynak
Chimia
WoS Q Değeri
Q3
Scopus Q Değeri
Q3
Cilt
73
Sayı
11
