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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

Article

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

DOI to cite this document: 10.5283/epub.58603


Abstract

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.



Involved Institutions


Details

Item typeArticle
Journal or Publication TitleAngewandte Chemie International Edition
PublisherWiley
Open Access TypeDEAL (Wiley)
Volume63
Number of Issue or Book Chapter28
Date1 May 2024
Date of publication04 Jul 2024 06:57
InstitutionsChemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf
Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Physical Chemistry I > Prof. Dr. Patrick Nürnberger
Identification Number
ValueType
10.1002/anie.202405780DOI
Keywordsphotoredox catalysis · cobalt · electron-transfer · arylation · quantum chemistry
Dewey Decimal Classification500 Science > 540 Chemistry & allied sciences
StatusPublished
RefereedYes, this version has been refereed
Created at the University of RegensburgPartially
URN of the UB Regensburgurn:nbn:de:bvb:355-epub-586032
Item ID58603

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