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Mechanistic studies indicated that the phosphine ligands could facilitate the decarboxylation of dioxazolones on the Fe center, and the hydrogen bonding interactions between the arylamines and the ligands on Fe nitrenoid intermediates might play a role in modulating the delicate interplay between the phosphine ligand, arylamine, and acyl nitrene N, favoring N\u2212N coupling over N\u2212P coupling. The new ligand\u2010promoted <jats:italic>N<\/jats:italic>\u2010amidation protocols offer a convenient way to access various challenging triazane compounds via double or sequential <jats:italic>N<\/jats:italic>\u2010amidation of primary arylamines.<\/jats:p>","DOI":"10.1002\/anie.202312465","type":"journal-article","created":{"date-parts":[[2023,11,24]],"date-time":"2023-11-24T06:47:32Z","timestamp":1700808452000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":47,"title":["Ligand\u2010Promoted Iron\u2010Catalyzed Nitrene Transfer for the Synthesis of Hydrazines and Triazanes through <i>N<\/i>\u2010Amidation of Arylamines"],"prefix":"10.1002","volume":"63","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-9751-2103","authenticated-orcid":false,"given":"Shi\u2010Yang","family":"Zhu","sequence":"first","affiliation":[{"name":"State Key Laboratory and Institute of Elemento-Organic Chemistry College of Chemistry Nankai University  Tianjin 300071 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wen\u2010Ji","family":"He","sequence":"additional","affiliation":[{"name":"State Key Laboratory and Institute of Elemento-Organic Chemistry College of Chemistry Nankai University  Tianjin 300071 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0005-2221-0927","authenticated-orcid":false,"given":"Guan\u2010Chi","family":"Shen","sequence":"additional","affiliation":[{"name":"State Key Laboratory and Institute of Elemento-Organic Chemistry College of Chemistry Nankai University  Tianjin 300071 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3623-7750","authenticated-orcid":false,"given":"Zi\u2010Qian","family":"Bai","sequence":"additional","affiliation":[{"name":"State Key Laboratory and Institute of Elemento-Organic Chemistry College of Chemistry Nankai University  Tianjin 300071 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3146-548X","authenticated-orcid":false,"given":"Fang\u2010Fang","family":"Song","sequence":"additional","affiliation":[{"name":"State Key Laboratory and Institute of Elemento-Organic Chemistry College of Chemistry Nankai University  Tianjin 300071 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9064-3418","authenticated-orcid":false,"given":"Gang","family":"He","sequence":"additional","affiliation":[{"name":"State Key Laboratory and Institute of Elemento-Organic Chemistry College of Chemistry Nankai University  Tianjin 300071 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3831-2988","authenticated-orcid":false,"given":"Hao","family":"Wang","sequence":"additional","affiliation":[{"name":"State Key Laboratory and Institute of Elemento-Organic Chemistry College of Chemistry Nankai University  Tianjin 300071 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5067-9889","authenticated-orcid":false,"given":"Gong","family":"Chen","sequence":"additional","affiliation":[{"name":"State Key Laboratory and Institute of Elemento-Organic Chemistry College of Chemistry Nankai University  Tianjin 300071 China"},{"name":"Frontiers Science Center for New Organic Matter Nankai University  Tianjin 300071 China"},{"name":"Haihe Laboratory of Sustainable Chemical Transformations  Tianjin 300192 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2023,12,6]]},"reference":[{"key":"e_1_2_7_1_1","unstructured":"Synthesis of N-containing compounds:"},{"key":"e_1_2_7_2_2","unstructured":"J. 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Liebman A. Greer The Chemistry of Nitrogen-Rich Functional Groups New York USA. John Wiley & Sons Ltd 2020."},{"key":"e_1_2_7_79_1","unstructured":"Selected reports on azanes including triazanes:"},{"key":"e_1_2_7_80_2","doi-asserted-by":"publisher","DOI":"10.1002\/hlca.19830660529"},{"key":"e_1_2_7_81_2","doi-asserted-by":"publisher","DOI":"10.1007\/s00894-007-0247-y"},{"key":"e_1_2_7_82_2","doi-asserted-by":"publisher","DOI":"10.1002\/cphc.201500560"},{"key":"e_1_2_7_83_2","doi-asserted-by":"publisher","DOI":"10.1016\/B978-0-08-100024-3.00014-3"},{"key":"e_1_2_7_84_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-0036-1591865"},{"key":"e_1_2_7_85_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202008798"},{"key":"e_1_2_7_86_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202009395"},{"key":"e_1_2_7_87_1","unstructured":"For selected reviews on constructing N\u2212N bonds:"},{"key":"e_1_2_7_88_2","doi-asserted-by":"publisher","DOI":"10.1039\/b010091a"},{"key":"e_1_2_7_89_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.200300416"},{"key":"e_1_2_7_90_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-0036-1588512"},{"key":"e_1_2_7_91_2","doi-asserted-by":"publisher","DOI":"10.1039\/D1SC03851F"},{"key":"e_1_2_7_92_1","unstructured":"Other selected examples of intermolecular N\u2212N coupling reactions:"},{"key":"e_1_2_7_93_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja5013323"},{"key":"e_1_2_7_94_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b05245"},{"key":"e_1_2_7_95_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c07272"},{"key":"e_1_2_7_96_1","unstructured":"Condensation or rearrangement reaction of dioxazolones:"},{"key":"e_1_2_7_97_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol9023387"},{"key":"e_1_2_7_98_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.9b01742"},{"key":"e_1_2_7_99_1","unstructured":"\u00a0"},{"key":"e_1_2_7_100_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.bmcl.2010.06.013"},{"key":"e_1_2_7_101_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.bmc.2014.10.011"},{"key":"e_1_2_7_102_1","unstructured":"The mechanism of theN-amidation of hydrazides with dioxazolones under tpy-promoted conditions has not been examined. At the moment it is unclear why the separate reaction of hydrazide with dioxazolones gives a lower yield of triazane than the one-pot doubleN-amidation setting. As shown in Figure\u20053B intermediate5FeP-pdt2needs to undergo protonolysis to release the final hydrazide product3\u2009a. We speculate that3\u2009amight be able to react with another dioxazolone to give the triazane product. Formation of intermediate5FeP-pdt2from hydrazide might be difficult under our reaction conditions. Nevertheless the triazane formation pathway via a nucleophilic attack of hydrazide to phosphine- orL6-bound Fe acyl nitrene intermediates cannot be ruled out."},{"key":"e_1_2_7_103_1","unstructured":"For two closely related N\u2212H\u22c5\u22c5\u22c5Cl hydrogen bonding in Fe complexes:"},{"key":"e_1_2_7_104_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00176a013"},{"key":"e_1_2_7_105_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201411399"},{"key":"e_1_2_7_106_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1099-0682(199907)1999:7<1103::AID-EJIC1103>3.0.CO;2-0"},{"key":"e_1_2_7_107_2","doi-asserted-by":"publisher","DOI":"10.1039\/D0CC07216H"},{"key":"e_1_2_7_108_1","unstructured":"\u00a0"},{"key":"e_1_2_7_109_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja110066j"},{"key":"e_1_2_7_110_2","doi-asserted-by":"publisher","DOI":"10.1039\/C3SC52533C"},{"key":"e_1_2_7_111_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202013499"},{"key":"e_1_2_7_112_2","doi-asserted-by":"publisher","DOI":"10.1007\/s11434-012-5151-x"},{"key":"e_1_2_7_113_1","unstructured":"We did not locate any suitable transition states for an N\u2212N coupling process that does not involve any hydrogen-bonding interaction between PhNH2and5Fe(=N)P."},{"key":"e_1_2_7_114_1","unstructured":"Deposition numbers2166614 (for62) and 2254336 (for63)contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum KarlsruheAccess Structures service."},{"key":"e_1_2_7_115_1","unstructured":"Our preliminary energy decomposition analyses (EDA) showed that5FeP(=N)N\u2032-TS2has a stronger total interaction energy than5FeP(=N)N\u2032-TS1(\u221220.5 vs \u221210.9\u2005kcal\/mol see more details in SI)."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202312465","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,2,3]],"date-time":"2025-02-03T13:51:27Z","timestamp":1738590687000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202312465"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,12,6]]},"references-count":115,"journal-issue":{"issue":"2","published-print":{"date-parts":[[2024,1,8]]}},"alternative-id":["10.1002\/anie.202312465"],"URL":"https:\/\/doi.org\/10.1002\/anie.202312465","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,12,6]]},"assertion":[{"value":"2023-08-25","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2023-12-06","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202312465"}}