Ambient Electroreductive Carboxylation of Unactivated Alkyl Chlorides and Polyvinyl Chloride (PVC) Upgrading

Abstract Electrosynthesis of alkyl carboxylic acids upon activating stronger alkyl chlorides at low‐energy cost is desired in producing carbon‐rich feedstock. Carbon dioxide (CO 2 ), a greenhouse gas, has been recognized as an ideal primary carbon source for those syntheses, and such events also mitigate the atmospheric CO 2 level, which is already alarming. On the other hand, the promising upcycling of polyvinyl chloride to polyacrylate is a high energy‐demanding carbon‐chloride (C−Cl) bond activation process. Molecular catalysts that can efficiently perform such transformation under ambient reaction conditions are rarely known. Herein, we reveal a nickel (Ni)‐pincer complex that catalyzes the electrochemical upgrading of polyvinyl chloride to polyacrylate in 95 % yield. The activities of such a Ni electrocatalyst bearing a redox‐active ligand were also tested to convert diverse examples of unactivated alkyl chlorides to their corresponding carboxylic acid derivatives. Furthermore, electronic structure calculations revealed that CO 2 binding occurs in a resting state to yield an η 2 ‐CO 2 adduct and that the C−Cl bond activation step is the rate‐determining transition state, which has an activation energy of 19.3 kcal/mol. A combination of electroanalytical methods, control experiments, and computational studies were also carried out to propose the mechanism of the electrochemical C−Cl activation process with the subsequent carboxylation step.