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Evidence of Sulfur Non‐Innocence in [Co(II)(dithiacyclam)](2+)‐Mediated Catalytic Oxygen Reduction Reactions
In many metalloenzymes, sulfur‐containing ligands participate in catalytic processes, mainly via the involvement in electron transfer reactions. In a biomimetic approach, we now demonstrate the implication of S‐ligation in cobalt mediated oxygen reduction reactions (ORR). A comparative study between...
Autores principales: | , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10108118/ https://www.ncbi.nlm.nih.gov/pubmed/36378951 http://dx.doi.org/10.1002/anie.202214074 |
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author | Battistella, Beatrice Iffland‐Mühlhaus, Linda Schütze, Maximillian Cula, Beatrice Kuhlmann, Uwe Dau, Holger Hildebrandt, Peter Lohmiller, Thomas Mebs, Stefan Apfel, Ulf‐Peter Ray, Kallol |
author_facet | Battistella, Beatrice Iffland‐Mühlhaus, Linda Schütze, Maximillian Cula, Beatrice Kuhlmann, Uwe Dau, Holger Hildebrandt, Peter Lohmiller, Thomas Mebs, Stefan Apfel, Ulf‐Peter Ray, Kallol |
author_sort | Battistella, Beatrice |
collection | PubMed |
description | In many metalloenzymes, sulfur‐containing ligands participate in catalytic processes, mainly via the involvement in electron transfer reactions. In a biomimetic approach, we now demonstrate the implication of S‐ligation in cobalt mediated oxygen reduction reactions (ORR). A comparative study between the catalytic ORR capabilities of the four‐nitrogen bound [Co(cyclam)](2+) (1; cyclam=1,5,8,11‐tetraaza‐cyclotetradecane) and the S‐containing analog [Co(S(2)N(2)‐cyclam)](2+) (2; S(2)N(2)‐cyclam=1,8‐dithia‐5,11‐diaza‐cyclotetradecane) reveals improved catalytic performance once the chalcogen is introduced in the Co coordination sphere. Trapping and characterization of the intermediates formed upon dioxygen activation at the Co(II) centers in 1 and 2 point to the involvement of sulfur in the O(2) reduction process as the key for the improved catalytic ORR capabilities of 2. |
format | Online Article Text |
id | pubmed-10108118 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-101081182023-04-18 Evidence of Sulfur Non‐Innocence in [Co(II)(dithiacyclam)](2+)‐Mediated Catalytic Oxygen Reduction Reactions Battistella, Beatrice Iffland‐Mühlhaus, Linda Schütze, Maximillian Cula, Beatrice Kuhlmann, Uwe Dau, Holger Hildebrandt, Peter Lohmiller, Thomas Mebs, Stefan Apfel, Ulf‐Peter Ray, Kallol Angew Chem Int Ed Engl Research Articles In many metalloenzymes, sulfur‐containing ligands participate in catalytic processes, mainly via the involvement in electron transfer reactions. In a biomimetic approach, we now demonstrate the implication of S‐ligation in cobalt mediated oxygen reduction reactions (ORR). A comparative study between the catalytic ORR capabilities of the four‐nitrogen bound [Co(cyclam)](2+) (1; cyclam=1,5,8,11‐tetraaza‐cyclotetradecane) and the S‐containing analog [Co(S(2)N(2)‐cyclam)](2+) (2; S(2)N(2)‐cyclam=1,8‐dithia‐5,11‐diaza‐cyclotetradecane) reveals improved catalytic performance once the chalcogen is introduced in the Co coordination sphere. Trapping and characterization of the intermediates formed upon dioxygen activation at the Co(II) centers in 1 and 2 point to the involvement of sulfur in the O(2) reduction process as the key for the improved catalytic ORR capabilities of 2. John Wiley and Sons Inc. 2022-12-29 2023-02-01 /pmc/articles/PMC10108118/ /pubmed/36378951 http://dx.doi.org/10.1002/anie.202214074 Text en © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc/4.0/ (https://creativecommons.org/licenses/by-nc/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes. |
spellingShingle | Research Articles Battistella, Beatrice Iffland‐Mühlhaus, Linda Schütze, Maximillian Cula, Beatrice Kuhlmann, Uwe Dau, Holger Hildebrandt, Peter Lohmiller, Thomas Mebs, Stefan Apfel, Ulf‐Peter Ray, Kallol Evidence of Sulfur Non‐Innocence in [Co(II)(dithiacyclam)](2+)‐Mediated Catalytic Oxygen Reduction Reactions |
title | Evidence of Sulfur Non‐Innocence in [Co(II)(dithiacyclam)](2+)‐Mediated Catalytic Oxygen Reduction Reactions |
title_full | Evidence of Sulfur Non‐Innocence in [Co(II)(dithiacyclam)](2+)‐Mediated Catalytic Oxygen Reduction Reactions |
title_fullStr | Evidence of Sulfur Non‐Innocence in [Co(II)(dithiacyclam)](2+)‐Mediated Catalytic Oxygen Reduction Reactions |
title_full_unstemmed | Evidence of Sulfur Non‐Innocence in [Co(II)(dithiacyclam)](2+)‐Mediated Catalytic Oxygen Reduction Reactions |
title_short | Evidence of Sulfur Non‐Innocence in [Co(II)(dithiacyclam)](2+)‐Mediated Catalytic Oxygen Reduction Reactions |
title_sort | evidence of sulfur non‐innocence in [co(ii)(dithiacyclam)](2+)‐mediated catalytic oxygen reduction reactions |
topic | Research Articles |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10108118/ https://www.ncbi.nlm.nih.gov/pubmed/36378951 http://dx.doi.org/10.1002/anie.202214074 |
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