Nitrile ligands activation in dinuclear aminocarbyne complexes

The diiron complexes [Fe(Cp)(CO){μ-η2:η2-C[N(Me)(R)]NC(C6H3R′)CCH(Tol)}Fe(Cp)(CO)] (R = Xyl, R′ = H, 3a; R = Xyl, R′ = Br, 3b; R = Xyl, R′ = OMe, 3c; R = Xyl, R′ = CO2Me, 3d; R = Xyl, R′ = CF3, 3e; R = Me, R′ = H, 3f; R = Me, R′ = CF3, 3g) are obtained in good yields from the reaction of [Fe2{μ-CN(Me)(R)}(μ-CO)(CO)(p-NCC6H4R′)(Cp)2]+ (R = Xyl, R′ = H, 2a; R = Xyl, R′ = Br, 2b; R = Xyl, R′ = OMe, 2c; R = Xyl, R′ = CO2Me, 2d; R = Xyl, R′ = CF3, 2e; R = Me, R′ = H, 2f; R = Me, R′ = CF3, 2g) with TolCCLi. The formation of 3 involves addition of the acetylide at the coordinated nitrile and C–N coupling with the bridging aminocarbyne together with orthometallation of the p-substituted aromatic ring and breaking of the Fe–Fe bond. Complexes3a–e which contain the N(Me)(Xyl) group exist in solution as mixtures of the E-trans and Z-trans isomers, whereas the compounds 3f,g, which posses an exocyclic NMe2 group, exist only in the Z-cis form. The crystal structures of Z-trans-3b, E-trans-3c, Z-trans-3e and Z-cis-3g have been determined by X-ray diffraction experiments.