Mechanistic insights into the visible-light-driven O-arylation of carboxylic acids catalyzed by xanthine-based nickel complexes

Rodriguez-Lugo, Rafael E. and Sander, Joan and Dietzmann, Simon and Rittner, Thomas and Rückel, Jannes and Landaeta, Vanessa R. and Park, Jiyong and Nuernberger, Patrick and Baik, Mu-Hyun and Wolf, Robert (2025) Mechanistic insights into the visible-light-driven O-arylation of carboxylic acids catalyzed by xanthine-based nickel complexes. CHEMICAL SCIENCE, 16 (6). pp. 2751-2762. ISSN 2041-6520, 2041-6539

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Abstract

We present a photocatalytic protocol for the O-arylation of carboxylic acids using nickel complexes bearing C8-pyridyl xanthines. Our studies suggest that the underlying mechanism operates independently of external photosensitizers. Stoichiometric experiments and crystallographic studies characterize the catalytically relevant Ni complexes. Spectroscopic and computational investigations propose a thermally controlled Ni(i)/Ni(iii) cycle followed by a photochemical regeneration of Ni(i) species. Furthermore, the pathways leading to the hydrodehalogenation of aryl halides, the comproportionation of Ni(i) and Ni(iii) species, the dimerization of Ni(i) intermediates and the influence of the counter ion on the cross-coupling reaction are unveiled. These investigations offer a comprehensive mechanistic understanding of the photocatalytic cross-coupling reaction catalyzed by a single Ni species and highlight key aspects of nickel-catalyzed metallaphotoredox reactions.

Item Type: Article
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: 06 May 2026 05:47
Last Modified: 06 May 2026 05:47
URI: https://pred.uni-regensburg.de/id/eprint/66562

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