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Journal of the Brazilian Chemical Society

versión impresa ISSN 0103-5053versión On-line ISSN 1678-4790

Resumen

BUSETTO, Luigi; MARCHETTI, Fabio; ZACCHINI, Stefano  y  ZANOTTI, Valerio. Reactions of diiron m-aminocarbyne complexes containing nitrile ligands. J. Braz. Chem. Soc. [online]. 2003, vol.14, n.6, pp.902-907. ISSN 0103-5053.  http://dx.doi.org/10.1590/S0103-50532003000600006.

The acetonitrile ligand in the m-aminocarbyne complexes [Fe2{m-CN(Me)R}(m-CO)(CO)(NCMe)(Cp)2][SO 3CF3] (R = Me, 2a, CH2Ph, 2b, Xyl, 2c) (Xyl = 2,6-Me2C6H3) is readily displaced by halides and cyanide anions affording the corresponding neutral species [Fe2{m-CN(Me)R}(m-CO)(CO)(X)(Cp)2 ] (X = Br, I, CN). Complexes 2 undergo deprotonation and rearrangement of the coordinated MeCN upon treatment with organolithium reagents. Trimethylacetonitrile, that does not contain acidic a hydrogens has been used in place of MeCN to form the complexes [Fe2{m-CN(Me)R}(m-CO)(CO)(NCCMe3 )(Cp)2][SO3CF3] (7a-c). Attempts to replace the nitrile ligand in 3 with carbon nucleophiles (by reaction with RLi) failed, resulting in decomposition products. However the reaction of 7c with LiCºCTol (Tol = C6H4Me), followed by treatment with HSO3CF3, yielded the imino complex [Fe2{m-CN(Me)Xyl}(m-CO)(CO) {N(H)C(CºCC6H4Me-4)CMe3}(Cp) 2][SO3CF3 ] (8), obtained via acetilyde addition at the coordinated NCCMe3.

Palabras clave : acetonitrile; nitrile activation; carbyne complexes; dinuclear complexes; C-C bond formation.

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