The equilibria and the kinetics of the binding of Iron(III) to salicylhydroxamic (SHA) and benzohydroxamic (BHA) acids have been investigated in aqueous solution (I = 1 M (HClO4/NaClO4), T = 298 K) using spectrophotometric and stopped-flow methods. Whereas Iron (III) forms a 1:1 complex (ML) with BHA, it forms both ML and M2L complexes with SHA. The presence of M2L in aqueous medium is corroborated by FTIR measurements. The reactive form of Iron(III) is the hydrolyzed species FeOH2+, which binds to the 0,0 site in ML and to the O,O and O-P,N (P = phenolate) sites in M2L, inducing full deprotonation of the latter. The reaction pathway is discussed in terms of a multistep mechanistic scheme in which the metal ligand interaction is coupled to hydrolysis and self-aggregation steps of Iron(III). The observation and characterization of M2L as a stable species is important because it contains the -Fe-O-N-Fe- sequence, which constitutes the repetitive motif of the SHA-based metallacrown ring and provides the rationale for 12-MC-4 metallacrowns. In the framework of this study, the kinetics of the Iron(III) dimerization and trimerization have also been investigated using the stopped-flow method to perform dilution jumps. The reaction scheme put forward involves two parallel steps (FeOH2+ + FeOH2+ and Fe3+ + FeOH2+) that lead to formation of the Fe-2(OH)(2)(4+) dimer and a slower step (FeOH2+ + Fe-2(OH)(2)(4+)) to form the trimer species. The kinetics of the last step have been investigated here for the first time, and the results deduced indicate that, of the two possible trimer structures reported in the literature, Fe-3(OH)(3)(6+) and Fe-3(OH)(4)(54+), the latter prevails by far.