Maersch, Julia and Reiter, Sebastian and Rittner, Thomas and Rodriguez-Lugo, Rafael E. and Whitfield, Maximilian and Scott, Daniel J. and Kutta, Roger Jan and Nuernberger, Patrick and de Vivie-Riedle, Regina and Wolf, Robert (2024) Cobalt-Mediated Photochemical C-H Arylation of Pyrroles. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 63 (28). ISSN 1433-7851, 1521-3773
Full text not available from this repository. (Request a copy)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 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. An octahedrally coordinated bis(diiminopyridine)cobalt complex enables the visible-light-driven arylation of pyrroles with chloro- and bromoarenes. Spectroscopic and computational studies elucidate the photoelectron transfer processes of the metal complex with triethylamine and a bromoarene, suggesting that electron transfer is facilitated by a preassembly of these molecules with the complex. image
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | DENSITY-FUNCTIONAL THEORY; CHARGE-TRANSFER EXCITATIONS; FITTING BASIS-SETS; PHOTOREDOX CATALYSIS; ELECTRON-TRANSFER; AMINOALKYL RADICALS; PERTURBATION-THEORY; METAL-COMPLEXES; EXCITED-STATES; HARTREE-FOCK; photoredox catalysis; cobalt; electron-transfer; arylation; quantum chemistry |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | 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 |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 16 Dec 2025 08:09 |
| Last Modified: | 16 Dec 2025 08:09 |
| URI: | https://pred.uni-regensburg.de/id/eprint/64039 |
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