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Mechanistic Investigations into the Selective Reduction of Oxygen by a Multicopper Oxidase T3 Site-Inspired Dicopper Complex
[Image: see text] Understanding how multicopper oxidases (MCOs) reduce oxygen in the trinuclear copper cluster (TNC) is of great importance for development of catalysts for the oxygen reduction reaction (ORR). Herein, we report a mechanistic investigation into the ORR activity of the dinuclear coppe...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10127274/ https://www.ncbi.nlm.nih.gov/pubmed/37123598 http://dx.doi.org/10.1021/acscatal.3c01143 |
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author | van Langevelde, Phebe H. Kounalis, Errikos Killian, Lars Monkcom, Emily C. Broere, Daniël L. J. Hetterscheid, Dennis G. H. |
author_facet | van Langevelde, Phebe H. Kounalis, Errikos Killian, Lars Monkcom, Emily C. Broere, Daniël L. J. Hetterscheid, Dennis G. H. |
author_sort | van Langevelde, Phebe H. |
collection | PubMed |
description | [Image: see text] Understanding how multicopper oxidases (MCOs) reduce oxygen in the trinuclear copper cluster (TNC) is of great importance for development of catalysts for the oxygen reduction reaction (ORR). Herein, we report a mechanistic investigation into the ORR activity of the dinuclear copper complex [Cu(2)L(μ-OH)](3+) (L = 2,7-bis[bis(2-pyridylmethyl)aminomethyl]-1,8-naphthyridine). This complex is inspired by the dinuclear T3 site found in the MCO active site and confines the Cu centers in a rigid scaffold. We show that the electrochemical reduction of [Cu(2)L(μ-OH)](3+) follows a proton-coupled electron transfer pathway and requires a larger overpotential due to the presence of the Cu-OH-Cu motif. In addition, we provide evidence that metal–metal cooperativity takes place during catalysis that is facilitated by the constraints of the rigid ligand framework, by identification of key intermediates along the catalytic cycle of [Cu(2)L(μ-OH)](3+). Electrochemical studies show that the mechanisms of the ORR and hydrogen peroxide reduction reaction found for [Cu(2)L(μ-OH)](3+) differ from the ones found for analogous mononuclear copper catalysts. In addition, the metal–metal cooperativity results in an improved selectivity for the four-electron ORR of more than 70% because reaction intermediates can be stabilized better between both copper centers. Overall, the mechanism of the [Cu(2)L(μ-OH)](3+)-catalyzed ORR in this work contributes to the understanding of how the cooperative function of multiple metals in close proximity can affect ORR activity and selectivity. |
format | Online Article Text |
id | pubmed-10127274 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-101272742023-04-26 Mechanistic Investigations into the Selective Reduction of Oxygen by a Multicopper Oxidase T3 Site-Inspired Dicopper Complex van Langevelde, Phebe H. Kounalis, Errikos Killian, Lars Monkcom, Emily C. Broere, Daniël L. J. Hetterscheid, Dennis G. H. ACS Catal [Image: see text] Understanding how multicopper oxidases (MCOs) reduce oxygen in the trinuclear copper cluster (TNC) is of great importance for development of catalysts for the oxygen reduction reaction (ORR). Herein, we report a mechanistic investigation into the ORR activity of the dinuclear copper complex [Cu(2)L(μ-OH)](3+) (L = 2,7-bis[bis(2-pyridylmethyl)aminomethyl]-1,8-naphthyridine). This complex is inspired by the dinuclear T3 site found in the MCO active site and confines the Cu centers in a rigid scaffold. We show that the electrochemical reduction of [Cu(2)L(μ-OH)](3+) follows a proton-coupled electron transfer pathway and requires a larger overpotential due to the presence of the Cu-OH-Cu motif. In addition, we provide evidence that metal–metal cooperativity takes place during catalysis that is facilitated by the constraints of the rigid ligand framework, by identification of key intermediates along the catalytic cycle of [Cu(2)L(μ-OH)](3+). Electrochemical studies show that the mechanisms of the ORR and hydrogen peroxide reduction reaction found for [Cu(2)L(μ-OH)](3+) differ from the ones found for analogous mononuclear copper catalysts. In addition, the metal–metal cooperativity results in an improved selectivity for the four-electron ORR of more than 70% because reaction intermediates can be stabilized better between both copper centers. Overall, the mechanism of the [Cu(2)L(μ-OH)](3+)-catalyzed ORR in this work contributes to the understanding of how the cooperative function of multiple metals in close proximity can affect ORR activity and selectivity. American Chemical Society 2023-04-12 /pmc/articles/PMC10127274/ /pubmed/37123598 http://dx.doi.org/10.1021/acscatal.3c01143 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | van Langevelde, Phebe H. Kounalis, Errikos Killian, Lars Monkcom, Emily C. Broere, Daniël L. J. Hetterscheid, Dennis G. H. Mechanistic Investigations into the Selective Reduction of Oxygen by a Multicopper Oxidase T3 Site-Inspired Dicopper Complex |
title | Mechanistic Investigations
into the Selective Reduction
of Oxygen by a Multicopper Oxidase T3 Site-Inspired Dicopper Complex |
title_full | Mechanistic Investigations
into the Selective Reduction
of Oxygen by a Multicopper Oxidase T3 Site-Inspired Dicopper Complex |
title_fullStr | Mechanistic Investigations
into the Selective Reduction
of Oxygen by a Multicopper Oxidase T3 Site-Inspired Dicopper Complex |
title_full_unstemmed | Mechanistic Investigations
into the Selective Reduction
of Oxygen by a Multicopper Oxidase T3 Site-Inspired Dicopper Complex |
title_short | Mechanistic Investigations
into the Selective Reduction
of Oxygen by a Multicopper Oxidase T3 Site-Inspired Dicopper Complex |
title_sort | mechanistic investigations
into the selective reduction
of oxygen by a multicopper oxidase t3 site-inspired dicopper complex |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10127274/ https://www.ncbi.nlm.nih.gov/pubmed/37123598 http://dx.doi.org/10.1021/acscatal.3c01143 |
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