{"doi":"10.1021/jacs.3c11032","title":"Selective Cobalt-Mediated Formation of Hydrogen Peroxide from Water under Mild Conditions via Ligand Redox Non-Innocence","abstract":"Despite the broad importance of hydrogen peroxide (H 2 O 2 ) in oxidative transformations, there are comparatively few viable routes for its production. The majority of commercial H 2 O 2 is currently produced by the stepwise reduction of dioxygen (O 2 ) via the anthraquinone process, but direct electrochemical formation from water (H 2 O) would have several advantages─namely, avoiding flammable gases or stepwise separations. However, the selective oxidation of H 2 O to form H 2 O 2 over the thermodynamically favored product of O 2 is a difficult synthetic challenge. Here, we present a molecular H 2 O oxidation system with excellent selectivity for H 2 O 2 that functions both stoichiometrically and catalytically. We observe high efficiency for electrocatalytic H 2 O 2 production at low overpotential with no O 2 observed under any conditions. Mechanistic studies with both calculations and kinetic analyses from isolated intermediates suggest that H 2 O 2 formation occurs in a bimolecular fashion via a dinuclear H 2 O 2 -bridged intermediate with an important role for a redox non-innocent ligand. This system showcases the ability of metal–ligand cooperativity and strategic design of the secondary coordination sphere to promote kinetically and thermodynamically challenging selectivity in oxidative catalysis.","journal":"Journal of the American Chemical Society","year":2024,"id":432754,"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":14,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9465,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"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":995579,"name":"Jan-Niklas Boyn","orcid":"0000-0002-6240-3759","position":1,"is_corresponding":false},{"id":995580,"name":"David A. Mazziotti","orcid":"0000-0002-9938-3886","position":2,"is_corresponding":false},{"id":588182,"name":"John S. Anderson","orcid":"0000-0002-0730-3018","position":3,"is_corresponding":false},{"id":730218,"name":"Sophie W. Anferov","orcid":"0000-0003-3972-5845","position":0,"is_corresponding":true}],"reference_count":71,"raw_metadata":null,"created_at":"2026-07-19T01:59:39.937122Z","pmid":"38375752","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":[]}