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Reactions of Mesityl Azide with Ferrocene-Based N-Heterocyclic Germylenes, Stannylenes and Plumbylenes, Including PPh₂-Functionalised Congeners

dc.date.accessioned2022-08-11T13:11:33Z
dc.date.available2022-08-11T13:11:33Z
dc.date.issued2022-05-05
dc.identifierdoi:10.17170/kobra-202207286541
dc.identifier.urihttp://hdl.handle.net/123456789/14046
dc.description.sponsorshipGefördert im Rahmen des Projekts DEALger
dc.language.isoeng
dc.rightsNamensnennung 4.0 International*
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/*
dc.subjectazideseng
dc.subjectcarbene homologueseng
dc.subjectmetalloceneseng
dc.subjectsubvalent compoundseng
dc.subjecttetryleneseng
dc.subject.ddc540
dc.titleReactions of Mesityl Azide with Ferrocene-Based N-Heterocyclic Germylenes, Stannylenes and Plumbylenes, Including PPh₂-Functionalised Congenerseng
dc.typeAufsatz
dcterms.abstractThe active PbII/P Lewis pair nature of a PPh₂-functionalised ferrocene-based N-heterocyclic plumbylene is demonstrated by its reaction with mesityl azide to afford a phosphazide, which is in contrast to the inertness of the unfunctionalised congener. The lighter analogues most likely react with MesN₃ at their respective tetrel atom Eᴵᴵ, leading to the formation of N₂ and an Eᶦᵛ=NMes unit, followed by NMes transfer from the Eᶦᵛ to the Pᴵᴵᴵ atom. The reactivity of ferrocene-based N-heterocyclic tetrylenes [{Fe(η⁵−C₅H₄−NSitBuMe₂)₂}E] (E=Ge, Sn, Pb) towards mesityl azide (MesN₃) is compared with that of PPh₂-functionalised congeners exhibiting two possible reaction sites, namely the Eᴵᴵ and Pᴵᴵᴵ atom. For E=Ge and Sn the reaction occurs at the Eᴵᴵ atom, leading to the formation of N₂ and an Eᶦᵛ=NMes unit. The germanimines are sufficiently stable for isolation. The stannanimines furnish follow-up products, either by [2+3] cycloaddition with MesN₃ or, in the PPh₂-substituted case, by NMes transfer from the Snᶦᵛ to the Pᴵᴵᴵ atom. Whereas [{Fe(η⁵−C₅H₄−NSitBuMe2)2}Pb] and other diaminoplumbylenes studied are inert even under forcing conditions, the PPh₂-substituted congener forms an addition product with MesN3, thus showing a behaviour similar to that of frustrated Lewis pairs. The germylenes of this study afford copper(I) complexes with CuCl, including the first structurally characterised linear dicoordinate halogenido complex [CuX(L)] with a heavier tetrylene ligand L.eng
dcterms.accessRightsopen accesseng
dcterms.creatorGuthardt, Robin
dcterms.creatorOetzel, Lisa
dcterms.creatorLang, Tobias
dcterms.creatorBruhn, Clemens
dcterms.creatorSiemeling, Ulrich
dc.relation.doidoi:10.1002/chem.202200996
dc.subject.swdAzideger
dc.subject.swdChemische Syntheseger
dc.subject.swdEisenkomplexeger
dc.subject.swdChemische Reaktionger
dc.subject.swdStaudinger-Reaktionger
dc.subject.swdCarbeneger
dc.type.versionpublishedVersion
dcterms.source.identifiereissn:1521-3765
dcterms.source.issueIssue 42
dcterms.source.journalChemistry - a European journaleng
dcterms.source.volumeVolume 28
kup.iskupfalse


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Except where otherwise noted, this item's license is described as Namensnennung 4.0 International