{"doi":"10.1021/jacs.2c05454","title":"A 4H<sup>+</sup>/4e<sup>–</sup> Electron-Coupled-Proton Buffer Based on a Mononuclear Cu Complex","abstract":"In this research article, we describe a 4H+/4e– electron-coupled-proton buffer (ECPB) based on Cu and a redox-active ligand. The protonated/reduced ECPB (complex 1: [Cu(8H+/14e–)]1+), consisting of CuI with 2 equiv of the ligand (catLH4: 1,1′-(4,5-dimethoxy-1,2-phenylene)bis(3-(tert-butyl)urea)), reacted with H+/e– acceptors such as O2 to generate the deprotonated/oxidized ECPB. The resulting compound, (complex 5: [Cu(4H+/10e–)]1+), was characterized by X-ray diffraction analysis, nuclear magnetic resonance (1H-NMR), and density functional theory, and it is electronically described as a cuprous bis(benzoquinonediimine) species. The stoichiometric 4H+/4e– reduction of 5 was carried out with H+/e– donors to generate 1 (CuI and 2 equiv of catLH4) and the corresponding oxidation products. The 1/5 ECPB system catalyzed the 4H+/4e– reduction of O2 to H2O and the dehydrogenation of organic substrates in a decoupled (oxidations and reductions are separated in time and space) and a coupled fashion (oxidations and reductions coincide in time and space). Mechanistic analysis revealed that upon reductive protonation of 5 and oxidative deprotonation of 1, fast disproportionation reactions regenerate complexes 5 and 1 in a stoichiometric fashion to maintain the ECPB equilibrium.","journal":"Journal of the American Chemical Society","year":2022,"id":271121,"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":13,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9616,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2022-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":936536,"name":"Khashayar Rajabimoghadam","orcid":null,"position":1,"is_corresponding":false},{"id":935957,"name":"Ankita Puri","orcid":"0000-0002-1783-3303","position":2,"is_corresponding":false},{"id":935958,"name":"David D. Hebert","orcid":"0000-0003-3999-7904","position":3,"is_corresponding":false},{"id":936537,"name":"Yi Lin Qiu","orcid":null,"position":4,"is_corresponding":false},{"id":936538,"name":"Sidney Eichelberger","orcid":null,"position":5,"is_corresponding":false},{"id":414296,"name":"Maxime A. Siegler","orcid":"0000-0003-4165-7810","position":6,"is_corresponding":false},{"id":782399,"name":"Marcel Swart","orcid":"0000-0002-8174-8488","position":7,"is_corresponding":false},{"id":340417,"name":"Michael P. Hendrich","orcid":"0000-0003-4775-0389","position":8,"is_corresponding":false},{"id":751414,"name":"Isaac Garcia‐Bosch","orcid":"0000-0002-6871-3029","position":9,"is_corresponding":false},{"id":239945,"name":"Tong Wu","orcid":"0000-0001-9968-9909","position":0,"is_corresponding":true}],"reference_count":35,"raw_metadata":null,"created_at":"2026-07-19T00:27:35.206187Z","pmid":"36083845","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":[]}