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Three types of nitrogenases have been described, named according to the heterometal in their cofactor: molybdenum, vanadium or iron nitrogenases. Spectroscopic and structural characterization allowed the unambiguous identification of the cofactors of molybdenum and vanadium nitrogenases and revealed a central \u03bc<jats:sub>6<\/jats:sub>\u2010carbide in both of them. Although genetic studies suggested that the cofactor of the iron nitrogenase contains a similar Fe<jats:sub>6<\/jats:sub>C core, this has not been experimentally demonstrated. Here we report Valence\u2010to\u2010Core X\u2010ray Emission Spectroscopy providing experimental evidence that this cofactor contains a carbide, thereby making the Fe<jats:sub>6<\/jats:sub>C core a feature of all nitrogenase cofactors.<\/jats:p>","DOI":"10.1002\/anie.202209190","type":"journal-article","created":{"date-parts":[[2022,8,17]],"date-time":"2022-08-17T12:07:40Z","timestamp":1660738060000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":25,"title":["An Fe<sub>6<\/sub>C Core in All Nitrogenase Cofactors"],"prefix":"10.1002","volume":"61","author":[{"given":"Laure","family":"Decamps","sequence":"first","affiliation":[{"name":"Department of Inorganic Spectroscopy Max Planck Institute for Chemical Energy Conversion  Stiftstrasse 34\u201336 45470 M\u00fclheim an der Ruhr Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Derek B.","family":"Rice","sequence":"additional","affiliation":[{"name":"Department of Inorganic Spectroscopy Max Planck Institute for Chemical Energy Conversion  Stiftstrasse 34\u201336 45470 M\u00fclheim an der Ruhr Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5196-3400","authenticated-orcid":false,"given":"Serena","family":"DeBeer","sequence":"additional","affiliation":[{"name":"Department of Inorganic Spectroscopy Max Planck Institute for Chemical Energy Conversion  Stiftstrasse 34\u201336 45470 M\u00fclheim an der Ruhr Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2022,9,7]]},"reference":[{"key":"e_1_2_3_1_1","unstructured":"\u00a0"},{"key":"e_1_2_3_2_2","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.77.12.7342"},{"key":"e_1_2_3_3_2","doi-asserted-by":"publisher","DOI":"10.1128\/jb.170.1.27-33.1988"},{"key":"e_1_2_3_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/cbic.202000022"},{"key":"e_1_2_3_5_1","unstructured":"\u00a0"},{"key":"e_1_2_3_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.biochem.7b01142"},{"key":"e_1_2_3_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.0c00067"},{"key":"e_1_2_3_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.9b00704"},{"key":"e_1_2_3_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.9b00650"},{"key":"e_1_2_3_10_1","unstructured":"\u00a0"},{"key":"e_1_2_3_11_2","doi-asserted-by":"publisher","DOI":"10.1128\/jb.168.2.673-682.1986"},{"key":"e_1_2_3_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.9b00489"},{"key":"e_1_2_3_13_1","first-page":"e01568","volume":"12","author":"P\u00e9rez-Gonz\u00e1lez A.","year":"2021","journal-title":"mBio"},{"key":"e_1_2_3_14_1","unstructured":"\u00a0"},{"key":"e_1_2_3_15_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF00292722"},{"key":"e_1_2_3_16_2","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.1411185111"},{"key":"e_1_2_3_17_1","unstructured":"\u00a0"},{"key":"e_1_2_3_18_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1206445"},{"key":"e_1_2_3_19_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1214025"},{"key":"e_1_2_3_20_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1224603"},{"key":"e_1_2_3_21_2","doi-asserted-by":"publisher","DOI":"10.1038\/ncomms9034"},{"key":"e_1_2_3_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja309254g"},{"key":"e_1_2_3_23_1","unstructured":"\u00a0"},{"key":"e_1_2_3_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201505930"},{"key":"e_1_2_3_24_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201505930"},{"key":"e_1_2_3_25_2","doi-asserted-by":"publisher","DOI":"10.1038\/nchembio.2428"},{"key":"e_1_2_3_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.0c01320"},{"key":"e_1_2_3_27_1","doi-asserted-by":"publisher","DOI":"10.1007\/s007750100263"},{"key":"e_1_2_3_28_1","unstructured":"\u00a0"},{"key":"e_1_2_3_29_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1256679"},{"key":"e_1_2_3_30_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202010790"},{"key":"e_1_2_3_30_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.202010790"},{"key":"e_1_2_3_31_2","doi-asserted-by":"crossref","unstructured":"M. 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