{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,11,2]],"date-time":"2026-11-02T18:49:55Z","timestamp":1793645395403,"version":"4.5.1"},"reference-count":92,"publisher":"Wiley","issue":"8","license":[{"start":{"date-parts":[[2024,12,13]],"date-time":"2024-12-13T00:00:00Z","timestamp":1734048000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001659","name":"Deutsche Forschungsgemeinschaft","doi-asserted-by":"publisher","award":["SCHU 1170\/11-2"],"award-info":[{"award-number":["SCHU 1170\/11-2"]}],"id":[{"id":"10.13039\/501100001659","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2025,2,6]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The Staudinger reaction provides chemists with a valuable tool for the reduction of azides, which are notoriously unstable and can decompose explosively. By providing a controlled method for the conversion of azides to amines, the reaction opened up new avenues for the synthesis of various amine\u2010containing compounds that are widely used in natural products, pharmaceuticals and polymers. The Staudinger reaction begins with the nucleophilic attack of a trivalent phosphine (usually triphenylphosphine), leading to the formation of a triazenide intermediate, a highly reactive species. Here we report how a divalent phosphorus\u2010centered biradicaloid reacts with covalent azides and show that it is possible to capture and fully characterize the transient intermediate. The experimental data is supported by quantum chemical calculations of the reaction paths and in terms of thermodynamics and chemical bonding.<\/jats:p>","DOI":"10.1002\/chem.202403893","type":"journal-article","created":{"date-parts":[[2024,11,27]],"date-time":"2024-11-27T10:28:57Z","timestamp":1732703337000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Isolation of a Staudinger\u2010type Intermediate Utilizing a Five\u2010Membered Phosphorus\u2010Centered Biradicaloid"],"prefix":"10.1002","volume":"31","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-6981-1042","authenticated-orcid":false,"given":"Y.","family":"Pilopp","sequence":"first","affiliation":[{"name":"Anorganische Chemie Institut f\u00fcr Chemie Universit\u00e4t Rostock  A.-Einstein-Str. 3a 18059 Rostock"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9450-3407","authenticated-orcid":false,"given":"J.","family":"Bresien","sequence":"additional","affiliation":[{"name":"Anorganische Chemie Institut f\u00fcr Chemie Universit\u00e4t Rostock  A.-Einstein-Str. 3a 18059 Rostock"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"K. P.","family":"L\u00fcdtke","sequence":"additional","affiliation":[{"name":"Anorganische Chemie Institut f\u00fcr Chemie Universit\u00e4t Rostock  A.-Einstein-Str. 3a 18059 Rostock"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9060-7065","authenticated-orcid":false,"given":"A.","family":"Schulz","sequence":"additional","affiliation":[{"name":"Anorganische Chemie Institut f\u00fcr Chemie Universit\u00e4t Rostock  A.-Einstein-Str. 3a 18059 Rostock"},{"name":"Leibniz Institut f\u00fcr Katalyse e.\u2009V.  Albert-Einstein-Str. 29a 18059 Rostock"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,12,13]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/hlca.19190020164"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/hlca.19210040192"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00996a027"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(01)92417-2"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(01)92229-X"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(00)00322-7"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200330070"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200400657"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201008102"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2008.08.009"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja044461m"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetlet.2003.12.117"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1039\/c0cc00426j"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201201400"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201304498"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201902710"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1039\/c0dt00015a"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2cc36782c"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja3110076"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201601224"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201511048"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201603954"},{"key":"e_1_2_8_23_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201612485"},{"key":"e_1_2_8_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.1c00638"},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9DT04517A"},{"key":"e_1_2_8_26_1","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.202000228"},{"key":"e_1_2_8_27_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201103742"},{"key":"e_1_2_8_28_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201403964"},{"key":"e_1_2_8_29_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201400143"},{"key":"e_1_2_8_30_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201410276"},{"key":"e_1_2_8_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b05596"},{"key":"e_1_2_8_32_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8DT03038C"},{"key":"e_1_2_8_33_1","first-page":"1","volume-title":"Comprehensive Inorganic Chemistry III","author":"Bresien J.","year":"2021"},{"key":"e_1_2_8_34_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8SC04893B"},{"key":"e_1_2_8_35_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2DT02229J"},{"key":"e_1_2_8_36_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202011886"},{"key":"e_1_2_8_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.3c03928"},{"key":"e_1_2_8_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.3c00255"},{"key":"e_1_2_8_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr400056a"},{"key":"e_1_2_8_40_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202300764"},{"key":"e_1_2_8_41_1","doi-asserted-by":"publisher","DOI":"10.1039\/c3dt50599e"},{"key":"e_1_2_8_42_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199505111"},{"key":"e_1_2_8_43_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr60283a003"},{"key":"e_1_2_8_44_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr00084a001"},{"key":"e_1_2_8_45_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2012.09.019"},{"key":"e_1_2_8_46_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3CS00290J"},{"key":"e_1_2_8_47_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200901472"},{"key":"e_1_2_8_48_1","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19901230425"},{"key":"e_1_2_8_49_1","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19921250208"},{"key":"e_1_2_8_50_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.77.3865"},{"key":"e_1_2_8_51_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.78.1396"},{"key":"e_1_2_8_52_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.478522"},{"key":"e_1_2_8_53_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.3382344"},{"key":"e_1_2_8_54_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.21759"},{"key":"e_1_2_8_55_1","doi-asserted-by":"publisher","DOI":"10.1039\/b508541a"},{"key":"e_1_2_8_56_1","doi-asserted-by":"publisher","DOI":"10.1039\/b515623h"},{"key":"e_1_2_8_57_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4773581"},{"key":"e_1_2_8_58_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.9b05734"},{"key":"e_1_2_8_59_1","doi-asserted-by":"publisher","DOI":"10.1021\/ct501129s"},{"key":"e_1_2_8_60_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4939030"},{"key":"e_1_2_8_61_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201503048"},{"key":"e_1_2_8_62_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9OB00615J"},{"key":"e_1_2_8_63_1","unstructured":"K. Tanaka A.\u2005R. Pradipta (RIKEN) EP4233916\u2005A1 2023."},{"key":"e_1_2_8_64_1","doi-asserted-by":"publisher","DOI":"10.1021\/om1007743"},{"key":"e_1_2_8_65_1","doi-asserted-by":"publisher","DOI":"10.1002\/cmdc.201500318"},{"key":"e_1_2_8_66_1","doi-asserted-by":"publisher","DOI":"10.1039\/c0dt00700e"},{"key":"e_1_2_8_67_1","doi-asserted-by":"publisher","DOI":"10.1107\/S2053273314026370"},{"key":"e_1_2_8_68_1","doi-asserted-by":"publisher","DOI":"10.1107\/S2053229614024218"},{"key":"e_1_2_8_69_1","unstructured":"G.\u2005M. Sheldrick SADABS Version 2 University of G\u00f6ttingen Germany 2004."},{"key":"e_1_2_8_70_1","unstructured":"Gaussian 09 Revision E.01 M.\u2005J. Frisch G.\u2005W. Trucks H.\u2005B. Schlegel G.\u2005E. Scuseria M.\u2005A. Robb J.\u2005R. Cheeseman G. Scalmani V. Barone B. Mennucci G.\u2005A. Petersson H. Nakatsuji M. Caricato X. Li H.\u2005P. Hratchian A.\u2005F. Izmaylov J. Bloino G. Zheng J.\u2005L. Sonnenberg M. Hada M. Ehara K. Toyota R. Fukuda J. Hasegawa M. Ishida T. Nakajima Y. Honda O. Kitao H. Nakai T. Vreven J.\u2005A. Montgomery Jr. J.\u2005E. Peralta F. Ogliaro M. Bearpark J.\u2005J. Heyd E. Brothers K.\u2005N. Kudin V.\u2005N. Staroverov T. Keith R. Kobayashi J. Normand K. Raghavachari A. Rendell J.\u2005C. Burant S.\u2005S. Iyengar J. Tomasi M. Cossi N. Rega J.\u2005M. Millam M. Klene J.\u2005E. Knox J.\u2005B. Cross V. Bakken C. Adamo J. Jaramillo R. Gomperts R.\u2005E. Stratmann O. Yazyev A.\u2005J. Austin R. Cammi C. Pomelli J.\u2005W. Ochterski R.\u2005L. Martin K. Morokuma V.\u2005G. Zakrzewski G.\u2005A. Voth P. Salvador J.\u2005J. Dannenberg S. Dapprich A.\u2005D. Daniels O. Farkas J.\u2005B. Foresman J.\u2005V. Ortiz J. Cioslowski D.\u2005J. Fox Gaussian Inc. Wallingford CT 2013."},{"key":"e_1_2_8_71_1","doi-asserted-by":"crossref","unstructured":"F. Neese The ORCA program system \u00a0Wiley Interdiscip. Rev.: Comput. Mol. Sci.\u00a02012 \u00a02 \u00a01 73\u201378.","DOI":"10.1002\/wcms.81"},{"key":"e_1_2_8_72_1","unstructured":"E.\u2005D. Glendening J.\u2005K. Badenhoop A.\u2005E. Reed J.\u2005E. Carpenter J.\u2005A. Bohmann C.\u2005M. Morales C.\u2005R. Landis F. Weinhold NBO 6.0 Theoretical Chemistry Institute University of Wisconsin Madison 2013."},{"key":"e_1_2_8_73_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-1-4684-7424-4_24"},{"key":"e_1_2_8_74_1","doi-asserted-by":"publisher","DOI":"10.1017\/CBO9780511614569"},{"key":"e_1_2_8_75_1","doi-asserted-by":"publisher","DOI":"10.1051\/jphysrad:01937008010039700"},{"key":"e_1_2_8_76_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRev.126.1028"},{"key":"e_1_2_8_77_1","doi-asserted-by":"publisher","DOI":"10.1080\/00268977400100711"},{"key":"e_1_2_8_78_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00179a005"},{"key":"e_1_2_8_79_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.471789"},{"key":"e_1_2_8_80_1","doi-asserted-by":"publisher","DOI":"10.1007\/s00214-007-0250-5"},{"key":"e_1_2_8_81_1","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2614(90)85472-O"},{"key":"e_1_2_8_82_1","doi-asserted-by":"publisher","DOI":"10.1039\/b000461h"},{"key":"e_1_2_8_83_1","doi-asserted-by":"publisher","DOI":"10.1021\/ct600110u"},{"key":"e_1_2_8_84_1","volume-title":"Essentials of Computational Chemistry: Theories and Models","author":"Cramer C. J.","year":"2004"},{"key":"e_1_2_8_85_1","doi-asserted-by":"publisher","DOI":"10.1016\/0039-6028(94)00731-4"},{"key":"e_1_2_8_86_1","doi-asserted-by":"publisher","DOI":"10.1142\/9789812839664_0016"},{"key":"e_1_2_8_87_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1323224"},{"key":"e_1_2_8_88_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1329672"},{"key":"e_1_2_8_89_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cpc.2016.04.001"},{"key":"e_1_2_8_90_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jctc.1c00462"},{"key":"e_1_2_8_91_1","doi-asserted-by":"publisher","DOI":"10.1016\/0166-1280(88)80248-3"},{"key":"e_1_2_8_92_1","unstructured":"Deposition number 2371934 (for3Br) contains the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service."}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.202403893","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T12:31:57Z","timestamp":1760272317000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.202403893"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,12,13]]},"references-count":92,"journal-issue":{"issue":"8","published-print":{"date-parts":[[2025,2,6]]}},"alternative-id":["10.1002\/chem.202403893"],"URL":"https:\/\/doi.org\/10.1002\/chem.202403893","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2024,12,13]]},"assertion":[{"value":"2024-10-22","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2024-12-13","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202403893"}}