{"doi":"10.1002/anie.202400273","title":"ATP‐Independent Turnover of Dinitrogen Intermediates Captured on the Nitrogenase Cofactor","abstract":"Abstract Nitrogenase reduces N 2 to NH 3 at its active‐site cofactor. Previous studies of an N 2 ‐bound Mo‐nitrogenase from Azotobacter vinelandii suggest binding of three N 2 species via asymmetric belt‐sulfur displacements in the two cofactors of its catalytic component (designated Av1*), leading to the proposal of stepwise N 2 reduction involving all cofactor belt‐sulfur sites; yet, the evidence for the existence of multiple N 2 species on Av1* remains elusive. Here we report a study of ATP‐independent, Eu II /SO 3 2− ‐driven turnover of Av1* using GC‐MS and frequency‐selective pulse NMR techniques. Our data demonstrate incorporation of D 2 ‐derived D by Av1* into the products of C 2 H 2 ‐ and H + ‐reduction, and decreased formation of NH 3 by Av1* concomitant with the release of N 2 under H 2 ; moreover, they reveal a strict dependence of these activities on SO 3 2− . These observations point to the presence of distinct N 2 species on Av1*, thereby providing strong support for our proposed mechanism of stepwise reduction of N 2 via belt‐sulfur mobilization.","journal":"Angewandte Chemie International Edition","year":2024,"id":454286,"datarank":0.31191623125197543,"base_score":2.0794415416798357,"endowment":2.0794415416798357,"self_citation_contribution":0.31191623125197543,"citation_network_contribution":0.0,"self_endowment_contribution":0.31191623125197543,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":7,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9425,"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":1277508,"name":"Martin Stang","orcid":"0000-0002-0781-8097","position":1,"is_corresponding":false},{"id":392492,"name":"Markus W. Ribbe","orcid":"0000-0002-7366-1526","position":2,"is_corresponding":false},{"id":392491,"name":"Yilin Hu","orcid":"0000-0002-9088-2865","position":3,"is_corresponding":false},{"id":392489,"name":"Chi Chung Lee","orcid":"0000-0002-5266-6686","position":0,"is_corresponding":true}],"reference_count":21,"raw_metadata":{"citation_network_status":"fetched"},"created_at":"2026-07-19T02:03:07.923686Z","pmid":"38527309","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":[]}