Metal rotaxane complexes of alpha-cyclodextrin (alpha-CD), [(NC)(5)Fe(pyz(CH2)(n)R.alpha-CD)Fe(CN)(5)](4-), have been prepared by the reactions of labile [Fe(CN)(5)OH2](3-) ions with pre-threaded dicationic bridging ligands [pyz(CH2)(n)R](2+) (pyz = pyrazinium, R = pyrazinium or 4,4’-bipyridinium (bpy), and n = 8-12) in aqueous solution. The stability constants for the alpha-CD inclusion of the ligands, as determined by H-1 NMR spectroscopy, increase with the chain length n and are slightly larger for R = 4,4’-bipyridinium than for pyrazinium head groups. The thermodynamic parameters for the pseudorotaxane equilibria may be correlated in terms of an enthalpy-entropy compensation effect, suggesting that substantial conformation changes and desolvation are involved in the inclusion and dissociation processes. The inclusion of the free ligand by alpha-CD decreases the rate constants for the formations of the monomeric and dimeric metal complexes from the [Fe(CN)(5)OH2](3-) ion. The rate constants for ligand dissociation of [pyz(CH2)(n)R](2+) from the metal complexes also decrease upon inclusion of the coordinated bridging ligand. The kinetics of the spontaneous self-assembly of the rotaxane upon mixing the dimer [(NC)(5)Fe(pyz(CH2)(n)R)Fe(CN)(5)](4-) and alpha-cyclodextrin are consistent with a rate-determining dissociation of a [Fe(CN)(5)](3-) unit, followed by alpha-CD inclusion of the semirotaxane and rapid recomplexation by a [Fe(CN)(5)OH2](3-) ion to form the rotaxane.