Evidence of Sulfur Non-Innocence in [Co II (dithiacyclam)] 2+ -Mediated Catalytic Oxygen Reduction Reactions.

Autor: Battistella B; Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489, Berlin, Germany., Iffland-Mühlhaus L; Faculty of Chemistry and Biochemistry, Ruhr-Universität Bochum, Universitätsstraße 150, 44780, Bochum, Germany., Schütze M; Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489, Berlin, Germany., Cula B; Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489, Berlin, Germany., Kuhlmann U; Institut für Chemie, Fakultät II, Technische Universität Berlin, Straße des 17. Juni 135, 10623, Berlin, Germany., Dau H; Institut für Physik, Freie Universität zu Berlin, Arnimallee 14, 14195, Berlin, Germany., Hildebrandt P; Institut für Chemie, Fakultät II, Technische Universität Berlin, Straße des 17. Juni 135, 10623, Berlin, Germany., Lohmiller T; Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489, Berlin, Germany.; EPR4Energy Joint Lab, Department Spins in Energy Conversion and Quantum Information Science, Helmholtz Zentrum Berlin für Materialien und Energie GmbH, Albert-Einstein-Str. 16, 12489, Berlin, Germany., Mebs S; Institut für Physik, Freie Universität zu Berlin, Arnimallee 14, 14195, Berlin, Germany., Apfel UP; Faculty of Chemistry and Biochemistry, Ruhr-Universität Bochum, Universitätsstraße 150, 44780, Bochum, Germany.; Department for Electrosynthesis, Fraunhofer Institute for Environmental, Safety and Energy Technology UMSICHT, Osterfelder Str. 3, 46047, Oberhausen, Germany., Ray K; Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489, Berlin, Germany.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2023 Feb 01; Vol. 62 (6), pp. e202214074. Date of Electronic Publication: 2022 Dec 29.
DOI: 10.1002/anie.202214074
Abstrakt: 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.
(© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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