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


Alberto, Roger; Iannuzzi, Marcella; Gurdal, Yeliz; Probst, Benjamin (2019). [CoII(BPyPy2COH)(OH2)2]2+: A Catalytic Pourbaix Diagram and AIMD Simulations on Four Key Intermediates. CHIMIA International Journal for Chemistry, 73(11):906-912.

Abstract

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.

Abstract

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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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
08 Research Priority Programs > Solar Light to Chemical Energy Conversion
Dewey Decimal Classification:540 Chemistry
Uncontrolled Keywords:General Chemistry, General Medicine
Language:English
Date:1 November 2019
Deposited On:07 Feb 2020 15:56
Last Modified:07 Feb 2020 15:56
Publisher:Swiss Chemical Society
ISSN:0009-4293
OA Status:Closed
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.2533/chimia.2019.906
Project Information:
  • : FunderSNSF
  • : Grant IDCRSII2_160801
  • : Project TitlePhotocatalytic Processes at Solvated Interfaces

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Embargo till: 2020-11-01