Rates of oxygen-isotope exchange between sites in the [HxTa6O19](8-x)-(aq) Lindqvist ion and aqueous solutions: comparisons to [HxNb6O19](8-x)-(aq)

Rates of steady oxygen-isotope exchange differ in interesting ways for two sets of structural oxygens in the HxTa6O19](8-x)-(aq) Lindqvist ion when compared to published data on the HxNb6O19]8-x(aq) version. Because of the lanthanide contraction, the HxTa6O19](8-x)-(aq) and HxNb6O19](8-x)-(aq) ions are virtually isostructural and differ primarily in a full core (Kr vs Xe) and the 4f14 electrons in the HxTa6O19](8-x)-(aq) ion. For both molecules, both pH-dependent and -independent pathways are evident in isotopic exchange of the 12 mu2-O(H) and 6 eta=O sites. Rate parameters for eta=O exchange at conditions where there is no pH dependence are, for the Ta(V) and Nb(V) versions respectively, K(298)(0) = 2.72 x 10(-5) s(-1) and 9.7 x 10(-6) s(-1), DeltaH = 83.6 +/- 3.2 and 89.4 kJ.mol(-1), and DeltaS = -51.0 +/- 10.6 and -42.9 J.mol(-1).K-1. For the mu2-O sites, K(298)(0) = 1.23 x 10(-6) s(-1), DeltaH = 70.3 +/- 9.7 and 88.0 kJ.mol(-1), and DeltaS = -116.1 +/- 32.7 and -29.4 J.mol(-1).K-1. Protonation of the 6 eta=O sites is energetically unfavored relative to the 12 mu2-O bridges in both molecules, although not equally so. Experimentally, protonation labilizes both the mu2-O(H) and eta=O sites to isotopic exchange in both molecules. Density-functional electronic-structure calculations indicate that proton affinities of structural oxygens in the two molecules differ with the HxTa6O19](8-x)-(aq) anion having a smaller affinity to protonate than the HxNb6O19]8-x(aq) ion. This difference in proton affinities is evident in the solution chemistry as pKa = 11.5 for the HTa6O19]7-(aq) ion and pKa = 13.6 for the HNb6O19]7-(aq) ion. Most striking is the observation that eta=O sites isotopically equilibrate faster than the mu2-O sites for the HxTa6O19](8-x)-(aq) Lindqvist ion but slower for the HxNb6O19](8-x)-(aq) ion, indicating that predictions about site reactivities in complicated structures, such as the interface of aqueous solutions and oxide solids, should be approached with great caution.