[1+1], [1+2], [2+1] or [3+1] acyclic and [1+1] or [2+2] cyclic Schiff bases (L A⋯L S), containing ferrocene moieties, have been prepared by reaction of formyl- or 1,1′-diformylferrocene and the appropriate amines. Formyl- and 1,1-diformylferrocene form respectively the acyclic [2+1] L W and [2+2] n L Z compounds by reaction with 1,4-diaminomethylbenzene. Similar compounds (L T⋯L V) have been obtained by condensation of aminomethylferrocene and 2,6-diformylpyridine, 2,6-diformyl-4-chlorophenol and 3-methoxy-2-hydroxybenzaldehyde. By reduction of these compounds with NaBH 4 the corresponding ferrocene–amine derivatives (L′) have been synthesized. All these compounds have been characterized by physico–chemical measurements (IR, NMR, Mössbauer spectroscopy and FAB mass spectrometry) and L H, derived by the condensation of ferrocene–aldehyde and 1,5-diamino-3-oxa-pentane, also by an X-ray structural determination. The X-ray analysis of crystals of L H, grown from a diethyl ether solution, shows that two independent molecules are present in the asymmetric unit; these two molecules are chemically equivalent with the ferrocenyl groups in the eclipsed form. The coordination ability of these compounds towards d metal ions as copper(II), nickel(II), platinum(II) and rhodium(III) was investigated; while the Schiff bases (L) may suffer hydrolysis, their reduced analogues (L′) form stable, well-defined complexes of the type M(L′)(Cl) n ( n=2, 3). The Mössbauer spectra of the prepared compounds show signals with δ at 0.44 and Δ E Q 2.30 mm s −1 for the Schiff bases L A⋯L S and 0.52 and 2.40 mm s −1 for the reduced analogues and hence may be diagnostic of the presence of Fe–CHN– or Fe–CH 2–NH– groups. The signals with δ at 0.51–0.55 and Δ E Q at 2.34–2.38 mm s −1 for the Schiff bases L T⋯L V, having Fe–CH 2–NCH groups, resemble those of the reduced analogues.