Kinetic studies on the ligand exchange of self-assembled M12L24 spherical complexes demonstrate that the multicomponent self-assembly roughly undergoes three stages. Initially, (i) there are very rapid equilibrations (ms(-1)) among the many components; (ii) as more stable structures are formed, the system equilibrates quickly (s(-1) to min(-1)) among the completed and uncompleted self-assemblies; misassembled structures are presumably corrected at this stage; and finally (iii) very stow equilibration (hours to days) at the final stage after the self-assembly completes, producing the kinetic stability of the whole. The half-lives of the ligand exchange processes in the M12L24 complexes are much longer than those for comparable monodentate Pd(II)-pyridine complexes by a factor of similar to 10(5), suggesting that, once formed, the 36-component molecular spheres behave like covalent componds.