246522-76-9Relevant academic research and scientific papers
The μ-sulfonium-methylidene diiron complexes [Fe2(μ-C(X)SMe2)(μ-CO)(CO)2(Cp) 2]SO3CF3 (X=CN, H) as precursors of μ-alkylidene complexes
Bordoni,Busetto,Cassani,Palazzi,Zanotti
, p. 333 - 340 (1999)
The reactions of [Fe2(μ-C(X)SMe2)(μ-CO)(CO)2(Cp) 2]SO3CF3 (X=CN 2a, H 2b; Cp=η-C5H5) with Li2Cu(CN)R2 (R=Me, Bun, Ph, CCC6H4Me-4, C4H3S) give the neutral μ-alkylidene complexes [Fe2(μ-C(X)R)(μ-CO)(CO)2(Cp)2] (3) arising from nucleophilic attack at the bridging carbon and SMe2 displacement. Likewise, 2a,b react with the sodium salt of dimethylmalonate, diethylmalonate, ethylacetoacetate, 2,4-pentanedione, dibenzoylmethane and benzylcyanide, resulting in the formation of the corresponding functionalized μ-alkylidene complexes [Fe2(μ-C(X)R)(μ-CO)(CO)2(Cp)2] (5-7) (X=CN, H; R=CH(COOMe)2, CH(COOEt)2, CH(COOMe)(COMe), CH(COMe)2, CH(COPh)2, CH(Ph)CN). The dichetone adducts [Fe2(μ-C(X)CH(COR)2)(μ-CO)(CO)2(Cp) 2] (X=CN, H; R=Me, Ph) undergo deacylation upon treatment with alumina, leading to the formation of the complexes [Fe2(μ-C(X)CH2C(O)R)(μ-CO)(CO)2(Cp) 2]. Reactions of 2a,b with LiBu or PhLi result in the formation the metallacycles [Fe2(μ-C(X)S(Me)CH2)(μ-CO)(CO)(CO)(Cp)2] (X=CN, 4a; H 4b) which arise from the deprotonation of an SMe group and the intramolecular addition at a terminally coordinated carbonyl. Finally, a comparison of the reactivity of 2a,b with that of the μ-carbyne diiron complexes [Fe2(μ-CX)(μ-CO)(CO)2(Cp)2]SO 3CF3 (X=H, SMe, NMe2) is presented.
