The acetonitrile ligand in the mu-aminocarbyne complexes [Fe-2{mu-CN(Me) R}(mu-CO)( CO)(NCMe)(Cp)(2)][SO3CF3] (R = Me, 2a, CH2Ph, 2b, Xyl, 2c) (Xyl = 2,6-Me2C6H3) is readily displaced by halides and cyanide anions affording the corresponding neutral species [Fe-2{mu-CN( Me) R}(mu-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 [Fe-2{mu-CN(Me)R}(mu-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 LiC= CTol (Tol = C6H4Me), followed by treatment with HSO3CF3, yielded the imino complex [Fe-2{mu-CN(Me) Xyl}(mu-CO)(CO) {N(H) C(C= CC6H4Me-4) CMe3}(Cp)(2)][SO3CF3] (8), obtained via acetilyde addition at the coordinated NCCMe3.

Reactions of diiron MU-aminocarbyne complexes containing nitrile ligands

MARCHETTI, FABIO;
2003-01-01

Abstract

The acetonitrile ligand in the mu-aminocarbyne complexes [Fe-2{mu-CN(Me) R}(mu-CO)( CO)(NCMe)(Cp)(2)][SO3CF3] (R = Me, 2a, CH2Ph, 2b, Xyl, 2c) (Xyl = 2,6-Me2C6H3) is readily displaced by halides and cyanide anions affording the corresponding neutral species [Fe-2{mu-CN( Me) R}(mu-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 [Fe-2{mu-CN(Me)R}(mu-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 LiC= CTol (Tol = C6H4Me), followed by treatment with HSO3CF3, yielded the imino complex [Fe-2{mu-CN(Me) Xyl}(mu-CO)(CO) {N(H) C(C= CC6H4Me-4) CMe3}(Cp)(2)][SO3CF3] (8), obtained via acetilyde addition at the coordinated NCCMe3.
2003
Busetto, L; Marchetti, Fabio; Zacchini, S; Zanotti, V.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11568/76285
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