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Märsch, Julia ; Reiter, Sebastian ; Rittner, Thomas ; Rodriguez‐Lugo, Rafael E. ; Whitfield, Maximilian ; Scott, Daniel J. ; Kutta, Roger Jan ; Nuernberger, Patrick ; de Vivie‐Riedle, Regina ; Wolf, Robert

Cobalt‐Mediated Photochemical C−H Arylation of Pyrroles

Märsch, Julia , Reiter, Sebastian, Rittner, Thomas, Rodriguez‐Lugo, Rafael E. , Whitfield, Maximilian, Scott, Daniel J. , Kutta, Roger Jan , Nuernberger, Patrick , de Vivie‐Riedle, Regina und Wolf, Robert (2024) Cobalt‐Mediated Photochemical C−H Arylation of Pyrroles. Angewandte Chemie International Edition 63 (28).

Veröffentlichungsdatum dieses Volltextes: 04 Jul 2024 06:57
Artikel
DOI zum Zitieren dieses Dokuments: 10.5283/epub.58603


Zusammenfassung

Precious metal complexes remain ubiquitous in photoredox catalysis (PRC) despite concerted efforts to find more earth-abundant catalysts and replacements based on 3d metals in particular. Most otherwise plausible 3d metal complexes are assumed to be unsuitable due to short-lived excited states, which has led researchers to prioritize the pursuit of longer excited-state lifetimes through careful ...

Precious metal complexes remain ubiquitous in photoredox catalysis (PRC) despite concerted efforts to find more earth-abundant catalysts and replacements based on 3d metals in particular. Most otherwise plausible 3d metal complexes are assumed to be unsuitable due to short-lived excited states, which has led researchers to prioritize the pursuit of longer excited-state lifetimes through careful molecular design. However, we report herein that the C−H arylation of pyrroles and related substrates (which are benchmark reactions for assessing the efficacy of photoredox catalysts) can be achieved using a simple and readily accessible octahedral bis(diiminopyridine) cobalt complex, [1-Co](PF6)2. Notably, [1-Co]2+ efficiently functionalizes both chloro- and bromoarene substrates despite the short excited-state lifetime of the key photoexcited intermediate *[1-Co]2+ (8 ps). We present herein the scope of this C−H arylation protocol and provide mechanistic insights derived from detailed spectroscopic and computational studies. These indicate that, despite its transient existence, reduction of *[1-Co]2+ is facilitated via pre-assembly with the NEt3 reductant, highlighting an alternative strategy for the future development of 3d metal-catalyzed PRC.



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Details

DokumentenartArtikel
Titel eines Journals oder einer ZeitschriftAngewandte Chemie International Edition
Verlag:Wiley
Band:63
Nummer des Zeitschriftenheftes oder des Kapitels:28
Datum1 Mai 2024
InstitutionenChemie und Pharmazie > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf
Chemie und Pharmazie > Institut für Physikalische und Theoretische Chemie > Lehrstuhl für Physikalische Chemie I > Prof. Dr. Patrick Nürnberger
Identifikationsnummer
WertTyp
10.1002/anie.202405780DOI
Stichwörter / Keywordsphotoredox catalysis · cobalt · electron-transfer · arylation · quantum chemistry
Dewey-Dezimal-Klassifikation500 Naturwissenschaften und Mathematik > 540 Chemie
StatusVeröffentlicht
BegutachtetJa, diese Version wurde begutachtet
An der Universität Regensburg entstandenZum Teil
URN der UB Regensburgurn:nbn:de:bvb:355-epub-586032
Dokumenten-ID58603

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