Aufsatz
A Stable Crystalline N-Heterocyclic Carbene with a 1,1’ - Ferrocenylene Backbone and Benzylic N-Substituents
Zusammenfassung
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.
Zitierform
In: Zeitschrift für anorganische und allgemeine Chemie : ZAAC = Journal of inorganic and general chemistry Volume 649 / Issue 4 (2022-12-08) eissn:1521-3749Förderhinweis
Gefördert im Rahmen des Projekts DEALZitieren
@article{doi:10.17170/kobra-202303067575,
author={Zinke, Julian and Bruhn, Clemens and Siemeling, Ulrich},
title={A Stable Crystalline N-Heterocyclic Carbene with a 1,1’ - Ferrocenylene Backbone and Benzylic N-Substituents},
journal={Zeitschrift für anorganische und allgemeine Chemie : ZAAC = Journal of inorganic and general chemistry},
year={2022}
}
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2023-03-06T14:15:31Z 2023-03-06T14:15:31Z 2022-12-08 doi:10.17170/kobra-202303067575 http://hdl.handle.net/123456789/14468 Gefördert im Rahmen des Projekts DEAL eng Namensnennung 4.0 International http://creativecommons.org/licenses/by/4.0/ 540 A Stable Crystalline N-Heterocyclic Carbene with a 1,1’ - Ferrocenylene Backbone and Benzylic N-Substituents Aufsatz 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. open access Zinke, Julian Bruhn, Clemens Siemeling, Ulrich doi:10.1002/zaac.202200334 Carbene Chemie publishedVersion eissn:1521-3749 Issue 4 Zeitschrift für anorganische und allgemeine Chemie : ZAAC = Journal of inorganic and general chemistry Volume 649 false e202200334
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