A Stable Crystalline N-Heterocyclic Carbene with a 1,1’ - Ferrocenylene Backbone and Benzylic N-Substituents
| dc.date.accessioned | 2023-03-06T14:15:31Z | |
| dc.date.available | 2023-03-06T14:15:31Z | |
| dc.date.issued | 2022-12-08 | |
| dc.identifier | doi:10.17170/kobra-202303067575 | |
| dc.identifier.uri | http://hdl.handle.net/123456789/14468 | |
| dc.description.sponsorship | Gefördert im Rahmen des Projekts DEAL | |
| dc.language.iso | eng | |
| dc.rights | Namensnennung 4.0 International | * |
| dc.rights.uri | http://creativecommons.org/licenses/by/4.0/ | * |
| dc.subject.ddc | 540 | |
| dc.title | A Stable Crystalline N-Heterocyclic Carbene with a 1,1’ - Ferrocenylene Backbone and Benzylic N-Substituents | eng |
| dc.type | Aufsatz | |
| dcterms.abstract | Two 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.accessRights | open access | |
| dcterms.creator | Zinke, Julian | |
| dcterms.creator | Bruhn, Clemens | |
| dcterms.creator | Siemeling, Ulrich | |
| dc.relation.doi | doi:10.1002/zaac.202200334 | |
| dc.subject.swd | Carbene | ger |
| dc.subject.swd | Chemie | ger |
| dc.type.version | publishedVersion | |
| dcterms.source.identifier | eissn:1521-3749 | |
| dcterms.source.issue | Issue 4 | |
| dcterms.source.journal | Zeitschrift für anorganische und allgemeine Chemie : ZAAC = Journal of inorganic and general chemistry | ger |
| dcterms.source.volume | Volume 649 | |
| kup.iskup | false | |
| dcterms.source.articlenumber | e202200334 |
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