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

A terminally coordinated CO ligand in the complexes [Fe2{m-CN(Me)R}(m-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 [Fe2{m-CN(Me)R}(m-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, L= NH(CH2)5, 10). In the absence of Me3NO, NH2Et gives addition at the CO ligand of 1b, yielding [Fe2{CN(Me)(Xyl)}(m-CO)(CO)C(O)NHEt(Cp)2] (11). Carbonyl replacement is also observed in the reaction of 1a-b with pyridine and benzophenone imine, affording [Fe2{m-CN(Me)R}(m-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-tolylacetylide leading to the formation of the m-vinylidene-diaminocarbene compound [Fe2-C=C(Tol)C(Ph)2N(H)CN(Me)(Xyl)(m-CO)(CO)(Cp2)] (15) which has been studied by X-ray diffraction.