Diiron-aminocarbyne complexes with amine or imine ligands:: C-N coupling between imine and aminocarbyne ligands promoted by tolylacetylide addition to [Fe2{[μ-CN(Me)R}([μ-CO)(CO)(NH=CPh2)(Cp)2][SO3CF3]

A terminally coordinated CO ligand in the complexes [Fe-2{mu-CN(Me)R (mu-CO)(CO)(2)(Cp)(2)][SO3CF3] (R = Me, 1a; R = Xyl, 1b; Xyl = 2,6-Me2C6H3), is readily displaced by primary and secondary amines (L), in the presence of Me3NO, affording the complexes [Fe-2{mu-CN(Me)R} (mu-CO)(CO)(L)(Cp)(2)][SO3CF3] (R = Me, L = NH2Et, 4a; R = Xyl, L = NH2Et, 4b; R = Me, L = NH2Pri, 5a; R = Xyl, L = NH2Pri. 5b: R = Xyl, L = NH2C6H11, 6; R = Xyl, L = NH2Ph, 7; R = Xyl, L = NH3, 8; R = Me, L = NHMe2, 9a; R = Xyl, L = NHMe2, 9b; R Xyl, = NH(CH2)(5), 10). In the absence of Me3NO, NH2Et gives addition at the CO ligand of 1b, yielding [Fe-2{mu-CN(Me)(Xyl)}(mu-CO)(CO){C(O)NHEt}(CP)(2)] (11). Carbonyl replacement is also observed in the reaction of lab with pyridine and benzophenone imine, affording [Fe-2{mu-CN(Me)R}(mu-CO)(CO)(L)(Cp)(2)][SO3CF3] (R = Me, L = Py, 12a; R = Xyl, L = Py, 12b; R = Me, L = HN=CPh2, 13a; R = Xyl, L = HN=CPh2,, 13b). The imino complex 13b reacts with p-totylacetylide leading to the formation of the mu-vinylidene-diaminocarbene compound [Fe-2{mu = eta(1):eta(2) - C=C(Tol)C(Ph)(2)N(H)CN(Me)(Xyl){(mu-CO)(CO)(Cp-2)] (15) which has been studied by X-ray diffraction. (C) 2004 Elsevier B.V. All rights reserved.