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The One\u2010electron oreduction of the related Ge<jats:sup>II<\/jats:sup>\u2212Fe<jats:sup>0<\/jats:sup> complex <jats:bold>3<\/jats:bold> leads to oxidative addition of one C\u2212P linkage of the <jats:sup>PhiP<\/jats:sup>Dipp ligand in an intermediary Fe<jats:sup>\u2212I<\/jats:sup> complex, leading to Fe<jats:sup>I<\/jats:sup> phosphide species <jats:bold>7<\/jats:bold>. One\u2010electron reduction reaction of <jats:bold>4<\/jats:bold> gives access to the iron(\u2212I) ferrato\u2010stannylene, <jats:bold>8<\/jats:bold>, giving evidence for the transient formation of such a species in the reduction of <jats:bold>3<\/jats:bold>. The covalently bound tin(II)\u2010iron(\u2212I) compound <jats:bold>8<\/jats:bold> has been characterised through EPR spectroscopy, SQUID magnetometry, and supporting computational analysis, which strongly indicate a high localization of electron spin density at Fe<jats:sup>\u2212I<\/jats:sup> in this unique d<jats:sup>9<\/jats:sup>\u2010iron complex.<\/jats:p>","DOI":"10.1002\/anie.202218141","type":"journal-article","created":{"date-parts":[[2023,2,9]],"date-time":"2023-02-09T12:01:32Z","timestamp":1675944092000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":33,"title":["Cationic Tetrylene\u2010Iron(0) Complexes: Access Points for Cooperative, Reversible Bond Activation and Open\u2010Shell Iron(\u2212I) Ferrato\u2010Tetrylenes**"],"prefix":"10.1002","volume":"62","author":[{"given":"Philip M.","family":"Keil","sequence":"first","affiliation":[{"name":"Fakult\u00e4t f\u00fcr Chemie Technische Universit\u00e4t M\u00fcnchen  Lichtenberg Strasse 4 85747 Garching Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ademola","family":"Soyemi","sequence":"additional","affiliation":[{"name":"Department of Chemical and Biological Engineering University of Alabama  Tuscaloosa AL 35487 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kilian","family":"Weisser","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie Humboldt-Universit\u00e4t zu Berlin  Brook-Taylor-Strasse 2 12489 Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tibor","family":"Szilv\u00e1si","sequence":"additional","affiliation":[{"name":"Department of Chemical and Biological Engineering University of Alabama  Tuscaloosa AL 35487 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Christian","family":"Limberg","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Chemie Humboldt-Universit\u00e4t zu Berlin  Brook-Taylor-Strasse 2 12489 Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4131-8870","authenticated-orcid":false,"given":"Terrance J.","family":"Hadlington","sequence":"additional","affiliation":[{"name":"Fakult\u00e4t f\u00fcr Chemie Technische Universit\u00e4t M\u00fcnchen  Lichtenberg Strasse 4 85747 Garching Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2023,3,22]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.196405801"},{"key":"e_1_2_7_1_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19640761405"},{"key":"e_1_2_7_2_1","unstructured":"\u00a0"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr60279a006"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-540-36930-1"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.8b00495"},{"key":"e_1_2_7_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202005434"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8CC02198H"},{"key":"e_1_2_7_8_1","unstructured":"For examples 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These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum KarlsruheAccess Structures service."},{"key":"e_1_2_7_54_1","unstructured":"\u00a0"},{"key":"e_1_2_7_55_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja410234x"},{"key":"e_1_2_7_56_2","doi-asserted-by":"publisher","DOI":"10.1039\/C7DT03301J"},{"key":"e_1_2_7_57_1","unstructured":"We note that the remainder of aromatic signals including those relating to the \u201cfree\u201d Dipp group of the NHC ligand are found as broad signal in the usual region between 6.9 and 8.0\u2005ppm."},{"key":"e_1_2_7_58_1","doi-asserted-by":"publisher","DOI":"10.1021\/j100785a001"},{"key":"e_1_2_7_59_1","unstructured":"\u00a0"},{"key":"e_1_2_7_60_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200353365"},{"key":"e_1_2_7_60_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200353365"},{"key":"e_1_2_7_61_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201204601"},{"key":"e_1_2_7_61_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201204601"},{"key":"e_1_2_7_62_1","unstructured":"\u00a0"},{"key":"e_1_2_7_63_2","doi-asserted-by":"publisher","DOI":"10.1038\/1821568a0"},{"key":"e_1_2_7_64_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.9b01459"},{"key":"e_1_2_7_65_1","unstructured":"Derived through DFT calculations. See Supporting Information for details."},{"key":"e_1_2_7_66_1","unstructured":"For examples of our earlier endeavours here see refs.\u2005[8] and [19]."},{"key":"e_1_2_7_67_1","unstructured":"\u00a0"},{"key":"e_1_2_7_68_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1109389"},{"key":"e_1_2_7_69_2","doi-asserted-by":"publisher","DOI":"10.1039\/b925794m"},{"key":"e_1_2_7_70_1","unstructured":"From these mixtures only very small amounts of the iron(II) amide compound PhiPDippFeNH2 could be isolated formed presumably through a complex ligand redistribution reaction."},{"key":"e_1_2_7_71_1","unstructured":"\u00a0"},{"key":"e_1_2_7_72_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja910305p"},{"key":"e_1_2_7_73_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b00159"},{"key":"e_1_2_7_74_1","unstructured":"Compound6isolated in this way always formed as a mixture with4 which could not be separated."},{"key":"e_1_2_7_75_1","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19921250413"},{"key":"e_1_2_7_76_1","unstructured":"\u00a0"},{"key":"e_1_2_7_77_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00823a061"},{"key":"e_1_2_7_78_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00446a022"},{"key":"e_1_2_7_79_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200701353"},{"key":"e_1_2_7_79_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200701353"},{"key":"e_1_2_7_80_1","unstructured":"For selected examples see:"},{"key":"e_1_2_7_81_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic50056a041"},{"key":"e_1_2_7_82_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1099-0682(199801)1998:1<119::AID-EJIC119>3.0.CO;2-X"},{"key":"e_1_2_7_83_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201411365"},{"key":"e_1_2_7_83_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201411365"},{"key":"e_1_2_7_84_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.0c02606"},{"key":"e_1_2_7_85_1","unstructured":"\u00a0"},{"key":"e_1_2_7_86_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201006918"},{"key":"e_1_2_7_86_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201006918"},{"key":"e_1_2_7_87_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja208675p"},{"key":"e_1_2_7_88_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201409454"},{"key":"e_1_2_7_88_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201409454"},{"key":"e_1_2_7_89_1","unstructured":"We note that the CV of3shows a relatively large peak separation \u0394Ep which is most likely due to the high concentration of this sample (3\u2005mM). To corroborate this a 3\u2005mM ferrocene sample was run under identical conditions also giving a large \u0394Epof 234\u2005mV (see Figure\u2005S59 in Supporting Information)."},{"key":"e_1_2_7_90_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr940053x"},{"key":"e_1_2_7_91_1","unstructured":"This would suggest that the reduced species has some degree of stability at ambient temperature on the timescale of the CV experiments (e.g. minutes). However due to challenges in generating and isolating this species through reduction using chemical methods the GeII\u2212Fe\u2212Ispecies (viz.7\u2032) could not be accessed in our hands."},{"key":"e_1_2_7_92_1","unstructured":"Spectrum referenced to a Mn2+standard see Supporting Information for details."},{"key":"e_1_2_7_93_1","unstructured":"\u00a0"},{"key":"e_1_2_7_94_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00273a025"},{"key":"e_1_2_7_95_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic3024953"},{"key":"e_1_2_7_96_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b12082"},{"key":"e_1_2_7_97_1","unstructured":"\u00a0"},{"key":"e_1_2_7_98_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00760a081"},{"key":"e_1_2_7_99_2","doi-asserted-by":"publisher","DOI":"10.1039\/D2DT01499H"},{"key":"e_1_2_7_100_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja030156"},{"key":"e_1_2_7_101_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b06845"},{"key":"e_1_2_7_102_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-540-88428-6"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202218141","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.202218141","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202218141","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2024,5,15]],"date-time":"2024-05-15T13:05:15Z","timestamp":1715778315000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202218141"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,3,22]]},"references-count":114,"journal-issue":{"issue":"19","published-print":{"date-parts":[[2023,5,2]]}},"alternative-id":["10.1002\/anie.202218141"],"URL":"https:\/\/doi.org\/10.1002\/anie.202218141","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,3,22]]},"assertion":[{"value":"2022-12-08","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2023-03-22","order":2,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202218141"}}