Hafnium complexes polynuclear

The extremely complicated aqueous solution chemistry of and HP has been reviewed by Larsen, Solovkin and Tsvetkova,and Clearfield. Zirconium(IV) and hafnium(IV) ions undergo extensive hydrolysis, and the predominant solution species are polynuclear, even in dilute (>10 -10 M) solutions of high acidity (1-2 M). Spectrophotometric, " ultracentrifugation, " and light scattering studies point to trinuclear and tetranuclear hydrolysis products complexes such as [M3(OH)4] and [M4(OH)8] have been suggested. ITie mononuclear ions are predominant solution species only at trace metal ion... 

Substitution at polynuclear aqua-ions is often much slower than at the respective parent mononuclear aqua-ions, as has been demonstrated for, e.g., aluminum(III), iron(III), zirconium(IV), and hafnium(IV). A further example has been provided by aluminum, where the Al,3 polynuclear oxo-aqua-species takes several months to equilibrate with lactate. Very different rates of complex formation are used to sort out speciation in multicomponent polynuclear/mononuclear aqua-cation systems. The problems involved in this approach are well illustrated by a Al NMR study of the numerous reaction pathways in the Al " /ferron [ferron = 7-iodo-8-hydroxyquinoline-5-sulfonic acid, (18)] reaction. The slowness of reaction of polynuclear species can cause difficulties in the determination of total metal content, e.g., of aluminum by ferron or Alizarin S (19), in natural waters. In certain situations these... 

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