Document Type
Article
Publication Date
3-7-2025
Publisher
American Chemical Society
Source Publication
ACS Catalysis
Source ISSN
2155-5435
Original Item ID
DOI: 10.1021/acscatal.4c07845
Abstract
Herein, we report the reaction development and mechanistic studies of visible-light-driven Cu-catalyzed dechlorination of trichloroacetic acid for the highly selective formation of monochloroacetic acid. Visible-light-driven transition metal catalysis via an inner-sphere pathway features the dual roles of transition metal species in photoexcitation and substrate activation steps, and a detailed mechanistic understanding of their roles is crucial for the further development of light-driven catalysis. This catalytic method, which features environmentally desired ascorbic acid as the hydrogen atom source and water/ethanol as the solvent, can be further applied to the dehalogenation of a variety of halocarboxylic acids and amides. Spectroscopic, X-ray crystallographic, and kinetic studies have revealed the detailed mechanism of the roles of copper in photoexcitation, thermal activation of the first C–Cl bond, and excited-state activation of the second C–Cl bond via excited-state chlorine atom transfer.
Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-No Derivative Works 4.0 International License.
Recommended Citation
Thillman, Abigail J.; Kill, Erin C.; Erickson, Alexander N.; and Wang, Dian, "Visible-Light-Driven Catalytic Dehalogenation of Trichloroacetic Acid and α-Halocarbonyl Compounds: Multiple Roles of Copper" (2025). Chemistry Faculty Research and Publications. 1093.
https://epublications.marquette.edu/chem_fac/1093
Comments
Published version. ACS Catalysis, Vol. 15, No. 5 (March 7, 2025): 3873-3881. DOI. © 2025 The Authors. Published by American Chemical Society. This article is licensed under CC-BY-NC-ND 4.0.