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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.
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| Item type | Article | ||||
| Journal or Publication Title | Angewandte Chemie International Edition | ||||
| Publisher | Wiley | ||||
| Open Access Type | DEAL (Wiley) | ||||
| Volume | 63 | ||||
| Number of Issue or Book Chapter | 28 | ||||
| Date | 1 May 2024 | ||||
| Date of publication | 04 Jul 2024 06:57 | ||||
| Institutions | Chemistry 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 |
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| Keywords | photoredox catalysis · cobalt · electron-transfer · arylation · quantum chemistry | ||||
| Dewey Decimal Classification | 500 Science > 540 Chemistry & allied sciences | ||||
| Status | Published | ||||
| Refereed | Yes, this version has been refereed | ||||
| Created at the University of Regensburg | Partially | ||||
| URN of the UB Regensburg | urn:nbn:de:bvb:355-epub-586032 | ||||
| Item ID | 58603 |
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