{"doi":"10.1002/cssc.202400517","title":"Ambient Electroreductive Carboxylation of Unactivated Alkyl Chlorides and Polyvinyl Chloride (PVC) Upgrading","abstract":"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.","journal":"ChemSusChem","year":2024,"id":480460,"datarank":0.0,"base_score":0.0,"endowment":0.0,"self_citation_contribution":0.0,"citation_network_contribution":0.0,"self_endowment_contribution":0.0,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":1,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.952,"is_data_producer":false,"deposit_databanks":null,"is_oa":false,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2024-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":1320046,"name":"Sandeep Kumar Dash","orcid":"0000-0002-5435-8556","position":1,"is_corresponding":false},{"id":789874,"name":"Jeanette A. Krause","orcid":"0000-0001-8098-8028","position":2,"is_corresponding":false},{"id":1320360,"name":"Soumalya Sinha","orcid":null,"position":3,"is_corresponding":false},{"id":751354,"name":"Julien A. Panetier","orcid":"0000-0003-4905-8396","position":4,"is_corresponding":false},{"id":1320047,"name":"Jianbing Jiang","orcid":"0000-0002-7466-522X","position":6,"is_corresponding":false},{"id":469653,"name":"Prasenjit Sarkar","orcid":"0000-0001-6459-3181","position":0,"is_corresponding":true}],"reference_count":80,"raw_metadata":null,"created_at":"2026-07-19T02:07:02.142014Z","pmid":"38890556","pmcid":null,"fwci":null,"citation_percentile":null,"influential_citations":0,"oa_status":null,"license":null,"views":0,"total_file_size_bytes":0,"version_count":0,"fair_f":null,"fair_a":null,"fair_i":null,"fair_r":null,"fair_zscore":null,"fair_rationale":null,"fair_model":null,"fair_agent_version":null,"fair_fulltext_source":null,"fair_has_llm":null,"fair_computed_at":null,"clinical_trials":[],"software_tools":[],"db_accessions":[],"linked_datasets":[],"topics":[]}