A Stable Crystalline N-Heterocyclic Carbene with a 1,1’ - Ferrocenylene Backbone and Benzylic N-Substituents

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dc.date.accessioned2023-03-06T14:15:31Z
dc.date.available2023-03-06T14:15:31Z
dc.date.issued2022-12-08
dc.description.sponsorshipGefördert im Rahmen des Projekts DEAL
dc.identifierdoi:10.17170/kobra-202303067575
dc.identifier.urihttp://hdl.handle.net/123456789/14468
dc.language.isoeng
dc.relation.doidoi:10.1002/zaac.202200334
dc.rightsNamensnennung 4.0 International*
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/*
dc.subject.ddc540
dc.subject.swdCarbeneger
dc.subject.swdChemieger
dc.titleA Stable Crystalline N-Heterocyclic Carbene with a 1,1’ - Ferrocenylene Backbone and Benzylic N-Substituentseng
dc.typeAufsatz
dc.type.versionpublishedVersion
dcterms.abstractTwo ferrocene-based NHCs of the type fc[(NR)₂C:] (1ᴿ; fc=1,1’-ferrocenylene) containing benzylic N-substituents were synthesised from the corresponding formamidinium compounds 1ᴿH[BF₄] by reaction with LiN(SiMe₃)₂. In the case of R=CH₂Ph (Bn), the carbene was characterised through trapping reactions with sulfur and selenium, which afforded fc[(NBn)₂CS] (1ᴮⁿS) and fc[(NBn)₂CSe] (1ᴮⁿSe), respectively. A thermally stable carbene was obtained with R=CH₂Mes (Bn*). Its reaction with sulfur and selenium afforded fc[(NBn*)₂CS] (1ᴮⁿ*S) and fc[(NBn*)₂CSe] (1ᴮⁿ*Se), respectively. Its reaction with [Rh(μ-Cl)(COD)]₂ (COD=cycloocta-1,5-diene), followed by substitution of the COD ligand by CO, furnished cis-[RhCl(CO)₂(1ᴮⁿ*)]. In combination with IR data of cis-[RhCl(CO)₂(1ᴮⁿ*)], NMR data of 1ᴮⁿ*H[BF₄], 1ᴮⁿ* and 1ᴮⁿ*Se indicate that 1ᴮⁿ* is substantially more nucleophilic and more electrophilic than conventional Arduengo carbenes, exhibiting an ambiphilicity similar to that of CAACs. The crystal structures of the formamidinium salts 1ᴿHX (X=[BF₄], R=Bn, Bn*; X=Cl, R=Bn*), of the carbene 1ᴮⁿ* and its Auˡ complex [AuCl(1ᴮⁿ*)] as well as of the sulfur and selenium derivatives 1ᴿE (E=S, Se; R=Bn, Bn*), the Rhˡ complexes cis-[RhCl(CO)₂(1ᴿ)] (R=Bn, Bn*) and the Cuˡ complex [CuBr(1ᴮⁿ)] were determined by single-crystal X-ray diffraction (XRD). In addition, the crystals structures of the diimine fc(N=CHMes)₂ and the diamine fc(NHBn*)₂ were also determined by XRD.eng
dcterms.accessRightsopen access
dcterms.creatorZinke, Julian
dcterms.creatorBruhn, Clemens
dcterms.creatorSiemeling, Ulrich
dcterms.source.articlenumbere202200334
dcterms.source.identifiereissn:1521-3749
dcterms.source.issueIssue 4
dcterms.source.journalZeitschrift für anorganische und allgemeine Chemie : ZAAC = Journal of inorganic and general chemistryger
dcterms.source.volumeVolume 649
kup.iskupfalse

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