{"doi":"10.1002/ange.202108135","title":"Surprising Condensation Reactions of the Azadithiolate Cofactor","abstract":"Abstract Azadithiolate, a cofactor found in all [FeFe]‐hydrogenases, is shown to undergo acid‐catalyzed rearrangement. Fe 2 [(SCH 2 ) 2 NH](CO) 6 self‐condenses to give Fe 6 [(SCH 2 ) 3 N] 2 (CO) 17 . The reaction, which is driven by loss of NH 4 + , illustrates the exchange of the amine group. X‐ray crystallography reveals that three Fe 2 (SR) 2 (CO) x butterfly subunits interconnected by the aminotrithiolate [N(CH 2 S) 3 ] 3− . Mechanistic studies reveal that Fe 2 [(SCH 2 ) 2 NR](CO) 6 participate in a range of amine exchange reactions, enabling new methodologies for modifying the adt cofactor. Ru 2 [(SCH 2 ) 2 NH](CO) 6 also rearranges, but proceeds further to give derivatives with Ru‐alkyl bonds Ru 6 [(SCH 2 ) 3 N][(SCH 2 ) 2 NCH 2 ]S(CO) 17 and [Ru 2 [(SCH 2 ) 2 NCH 2 ](CO) 5 ] 2 S.","journal":"Angewandte Chemie","year":2021,"id":229264,"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":0,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9485,"is_data_producer":false,"deposit_databanks":null,"is_oa":false,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2021-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":445550,"name":"Casseday P. Richers","orcid":"0000-0002-1324-0447","position":1,"is_corresponding":false},{"id":378738,"name":"Toby J. Woods","orcid":"0000-0002-1737-811X","position":2,"is_corresponding":false},{"id":225328,"name":"Thomas B. Rauchfuss","orcid":"0000-0003-2547-5128","position":3,"is_corresponding":false},{"id":738790,"name":"Fanjun Zhang","orcid":"0000-0001-7587-6857","position":0,"is_corresponding":true}],"reference_count":26,"raw_metadata":null,"created_at":"2026-07-18T23:54:57.922333Z","pmid":null,"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":[]}