Cargando…

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...

Descripción completa

Detalles Bibliográficos
Autores principales: Battistella, Beatrice, Iffland‐Mühlhaus, Linda, Schütze, Maximillian, Cula, Beatrice, Kuhlmann, Uwe, Dau, Holger, Hildebrandt, Peter, Lohmiller, Thomas, Mebs, Stefan, Apfel, Ulf‐Peter, Ray, Kallol
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
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
_version_ 1785026780970614784
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
work_keys_str_mv AT battistellabeatrice evidenceofsulfurnoninnocenceincoiidithiacyclam2mediatedcatalyticoxygenreductionreactions
AT ifflandmuhlhauslinda evidenceofsulfurnoninnocenceincoiidithiacyclam2mediatedcatalyticoxygenreductionreactions
AT schutzemaximillian evidenceofsulfurnoninnocenceincoiidithiacyclam2mediatedcatalyticoxygenreductionreactions
AT culabeatrice evidenceofsulfurnoninnocenceincoiidithiacyclam2mediatedcatalyticoxygenreductionreactions
AT kuhlmannuwe evidenceofsulfurnoninnocenceincoiidithiacyclam2mediatedcatalyticoxygenreductionreactions
AT dauholger evidenceofsulfurnoninnocenceincoiidithiacyclam2mediatedcatalyticoxygenreductionreactions
AT hildebrandtpeter evidenceofsulfurnoninnocenceincoiidithiacyclam2mediatedcatalyticoxygenreductionreactions
AT lohmillerthomas evidenceofsulfurnoninnocenceincoiidithiacyclam2mediatedcatalyticoxygenreductionreactions
AT mebsstefan evidenceofsulfurnoninnocenceincoiidithiacyclam2mediatedcatalyticoxygenreductionreactions
AT apfelulfpeter evidenceofsulfurnoninnocenceincoiidithiacyclam2mediatedcatalyticoxygenreductionreactions
AT raykallol evidenceofsulfurnoninnocenceincoiidithiacyclam2mediatedcatalyticoxygenreductionreactions