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Lookup NU author(s): Dr Dominic Shiels, Dr Magda Pascual-BorrasORCiD, Dr John ErringtonORCiD
This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).
Understanding how modification of molecular structures changes the thermochemistry of H atom uptake can provide design criteria for the formation of highly active catalysts for reductive transformations. Herein, we describe the effect of doping an atomically precise polyoxotungstate with vanadium on proton-coupled electron transfer (PCET) reactivity. The Lindqvist-type polyoxotungstate [W6O19]2–displays reversible redox chemistry, which was found to be unchanged in the presence of acid, indicating an inability to couple reduction with protonation. However, the incorporation of a single vanadium center into the structure significantly changes the reactivity, and the potential required for one-electron reduction of [VW5O19]3– was shown to vary with the strength of the acid added. Construction of a potential-pKadiagram allowed assessment of the thermodynamics of H atom uptake, indicating BDFE(O–H) ≈ 64 kcal/mol, while chemical synthesis of the reduced/protonated derivative (TBA)3[VW5O19H] was used to probe the position of protonation. tures changes the thermochemistry of H atom uptake can providedesign criteria for the formation of highly active catalysts for reductivetransformations. Herein, we describe the effect of doping anatomically precise polyoxotungstate with vanadium on proton-coupledelectron transfer (PCET) reactivity. The Lindqvist-type polyoxotung-state [W6O19]2− displays reversible redox chemistry, which was foundto be unchanged in the presence of acid, indicating an inability tocouple reduction with protonation. However, the incorporation of asingle vanadium center into the structure significantly changes thereactivity, and the potential required for one-electron reduction of[VW5O19]3− was shown to vary with the strength of the acid added.Construction of a potential-pUnderstanding how modification of molecular struc-tures changes the thermochemistry of H atom uptake can providedesign criteria for the formation of highly active catalysts for reductivetransformations. Herein, we describe the effect of doping anatomically precise polyoxotungstate with vanadium on proton-coupledelectron transfer (PCET) reactivity. The Lindqvist-type polyoxotung-state [W6O19]2− displays reversible redox chemistry, which was foundto be unchanged in the presence of acid, indicating an inability tocouple reduction with protonation. However, the incorporation of asingle vanadium center into the structure significantly changes thereactivity, and the potential required for one-electron reduction of[VW5O19]3− was shown o vary with the strength of the acid added.Construction of a potential-pKa diagram allowed assessment of thethermodynamics of H atom uptake, indicating BDFE(O−H) ≈ 64 kcal/mol, while chemical synthesis of the reduced/protonatedderivative (TBA)3[VW5O19H] was used to probe the position of protoKa diagram allowed assessment of thethermodynamics of H atom uptake, indicating BDFE(O−H) ≈ 64 kcal/mol, while chemical synthesis of the reduced/protonatedderivative (TBA)3[VW5O19H] was used to probe the position of protonation.
Author(s): Shiels D, Lu Z, Pascual-Borràs M, Cajiao N, Marinho TV, Brennessel MW, Neidig ML, Errington RJ, Matson EM
Publication type: Article
Publication status: Published
Journal: Inorganic Chemistry
Year: 2024
Volume: 63
Issue: 49
Pages: 23304–23316
Online publication date: 20/11/2024
Acceptance date: 07/11/2024
Date deposited: 20/11/2024
ISSN (print): 0020-1669
ISSN (electronic): 1520-510X
Publisher: American Chemical Society
URL: https://doi.org/10.1021/acs.inorgchem.4c03873
DOI: 10.1021/acs.inorgchem.4c03873
Data Access Statement: The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.4c03873. Additional characterization data of materials, crystallographic information, and details about computational methods used in this work (PDF) ic4c03873_si_001.pdf (3.17 MB) Accession Codes Deposition Numbers 2383610–2383612 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via the joint Cambridge Crystallographic Data Centre (CCDC) and Fachinformationszentrum Karlsruhe Access Structures service.
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