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

Electrosynthesis of alkyl carboxylic acids upon activating stronger alkyl chlorides at low-energy cost is desired in producing carbon-rich feedstock. Carbon dioxide (CO₂), a greenhouse gas, has been recognized as an ideal primary carbon source for those syntheses, and such events also mitigate the atmospheric CO₂ 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 CO₂ binding occurs in a resting state to yield an η²-CO₂ 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.