The reaction of 3-aminoprop-1-ene (allylamine) with the etherate complexes [(n5-C5R5)(CO)2Fe(L)]+(R = H; L = Et2O; R = CH3; L = THF) have been investigated and found to give air stable allylamino com-plexes [(n5-C5R5)(CO)2Fe(NH2CH2 CH=CH2)]+(R = H (3)orCH3(4)) with the vinyl functionality pendant on the alkyl chain. These complexes have been isolated as the tetrafluoroborate salts. They undergo halogenation reactions on the pendant vinyl group to give high yields of the dihalopropylamino complexes [(g5-C5H5)(CO)2Fe{NH2CH2CH(X)CH2X}]+(X = Cl (5), Br (6)) and [{n5C5(CH3)5}(CO) 2-Fe{NH2CH2CH(Br)CH2Br}]+,(7), respectively. Complexes3and4also react with the etherate complexes[(g5-C5R5)(CO) 2Fe(L)]+to yield dinuclear complexes of the type, [(n5-C5R5)(CO)2Fe(NH2CH2CH=CH2)Fe(-CO)2(n5-C5R50)]2+(R not necessarily equal to R0), in which the two iron moieties are in different electronic environments. The NMR and IR data of the dinuclear complexes show that the allylamine ligand bridges the two metal systems. It is coordinated to the metal on one end via the nitrogen of the amine function-ality in ag1-fashion and on the other end via the vinylic functionality in a n2 -fashion forming a chiral metallacyclopropane type structure. The reaction of the dinuclear salt [{(n5-C5H5)(CO)2-Fe}2(NH2CH2CH=CH2)](BF4)2 with NaI in acetone gives [(n5-C5H5)(CO)2Fe(NH2CH2CH=CH2)]I and[(n5-C5H5)Fe(CO)2I] indicating that the iodide displaces the n2-coordinated metal center. All these com-pounds have been fully characterized. The molecular structures of [3][BF4], [4][BF4] and [7][BF4] have been determined by single crystal X-ray diffraction