The reactions of 2-thienyllithium (Lith) with a variety of carbyne complexes result in C-C bond formation at different sites of the molecules. The thiocarbyne cis-[Fe2(μ-CSMe)(μ-CS)(CO)2(Cp)2] + 1 (Cp = η-C5H5) underwent Cp addition forming [Fe2(μ-CSMe)(μ-CS)(CO)2(Cp)(η4-C 5H5th)] 3 and trace amounts of [Fe2(μ-CSMe)(μ-CS)-{C(O)th}(CO)(Cp)2] 4. By contrast all the aminocarbynes [Fe2(μ-CNRR′)(μ-CO)(CO)2(Cp)2] + (R = R′ = Me 2a; R = Me, R′ = PhCH2 2b) and [Ru2(μ-CNMe2)(μ-CO)(CO)2(Cp) 2]+ 6 gave the corresponding acyl derivatives [M2-(μ-CNRR′)(μ-CO)(CO){C(O)th}(Cp)2] (M = Fe 5a and 5b; R = R′ = Me, M = Ru 7). When R ≠ R′, the NMR spectra of these neutral species show the presence of two isomers α and β arising from hindered rotation around the μ-C=N bond. The relevance of these reactions is discussed in terms of selective C-C bond formation in comparison with analogous carbon nucleophile addition at [Fe2(μ-CSMe)(μ-CO)(CO)2(Cp)2] +. The crystal structures of 3 and [Fe2{μ-CN(Me)CH2Ph}(μ-CO)(CO){C(O)th}(Cp) 2] 5b are reported and discussed. The conformation of the Fe2C2 diamond is shown to depend on the nature of the bridging ligands. Simple models of electronic structure are outlined on the basis of the geometric evidence.

Albano V.G., Bordoni S., Busetto L., Camiletti C., Monari M., Palazzi A., et al. (1997). Carbon-carbon bond formation in the reactions of diiron μ-carbyne complexes with 2-thienyllithium, synthesis and structural characterization. JOURNAL OF THE CHEMICAL SOCIETY DALTON TRANSACTIONS, 1(24), 4665-4670 [10.1039/a705245f].

Carbon-carbon bond formation in the reactions of diiron μ-carbyne complexes with 2-thienyllithium, synthesis and structural characterization

Bordoni S.;Monari M.;
1997

Abstract

The reactions of 2-thienyllithium (Lith) with a variety of carbyne complexes result in C-C bond formation at different sites of the molecules. The thiocarbyne cis-[Fe2(μ-CSMe)(μ-CS)(CO)2(Cp)2] + 1 (Cp = η-C5H5) underwent Cp addition forming [Fe2(μ-CSMe)(μ-CS)(CO)2(Cp)(η4-C 5H5th)] 3 and trace amounts of [Fe2(μ-CSMe)(μ-CS)-{C(O)th}(CO)(Cp)2] 4. By contrast all the aminocarbynes [Fe2(μ-CNRR′)(μ-CO)(CO)2(Cp)2] + (R = R′ = Me 2a; R = Me, R′ = PhCH2 2b) and [Ru2(μ-CNMe2)(μ-CO)(CO)2(Cp) 2]+ 6 gave the corresponding acyl derivatives [M2-(μ-CNRR′)(μ-CO)(CO){C(O)th}(Cp)2] (M = Fe 5a and 5b; R = R′ = Me, M = Ru 7). When R ≠ R′, the NMR spectra of these neutral species show the presence of two isomers α and β arising from hindered rotation around the μ-C=N bond. The relevance of these reactions is discussed in terms of selective C-C bond formation in comparison with analogous carbon nucleophile addition at [Fe2(μ-CSMe)(μ-CO)(CO)2(Cp)2] +. The crystal structures of 3 and [Fe2{μ-CN(Me)CH2Ph}(μ-CO)(CO){C(O)th}(Cp) 2] 5b are reported and discussed. The conformation of the Fe2C2 diamond is shown to depend on the nature of the bridging ligands. Simple models of electronic structure are outlined on the basis of the geometric evidence.
1997
Albano V.G., Bordoni S., Busetto L., Camiletti C., Monari M., Palazzi A., et al. (1997). Carbon-carbon bond formation in the reactions of diiron μ-carbyne complexes with 2-thienyllithium, synthesis and structural characterization. JOURNAL OF THE CHEMICAL SOCIETY DALTON TRANSACTIONS, 1(24), 4665-4670 [10.1039/a705245f].
Albano V.G.; Bordoni S.; Busetto L.; Camiletti C.; Monari M.; Palazzi A.; Prestopino F.; Zanotti V.
File in questo prodotto:
Eventuali allegati, non sono esposti

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/898977
 Attenzione

Attenzione! I dati visualizzati non sono stati sottoposti a validazione da parte dell'ateneo

Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 30
  • ???jsp.display-item.citation.isi??? 25
social impact