The racemization/symmetrization of helicate- or meso-helicate-type dinuclear titanium(IV) complexes M-n[(ligand)(3)Ti-2] (n = 4: M = Li, Na, K, Cs; n = 2: M = Ca, Sr), which are formed by metal-directed self-assembly of alkyl-bridged bis(catecholate) ligands in the presence of basic alkali-metal or alkaline-earth metal salts, can be monitored by dynamic NMR spectroscopy. The free-energy barrier (Delta G(not equal)) of this process is influenced by the nature of the ligand, the solvent, and the counterion.