Preparation and isolation of mono-Nb substituted Keggin-type phosphomolybdic acid and its application as an oxidation catalyst for isobutylaldehyde and Wacker-type oxidation.

The potassium and proton mixed salt of mono-Nb substituted Keggin-type phosphomolybdate, KH3[PMo11NbO40], was isolated in a pure form by reacting Keggin-type phosphomolybdic acid (H3[PMo12O40]) and potassium hexaniobate (K8Nb6O19) in water, followed by freeze-drying. The all protonic form, H4[PMo11NbO40], was isolated via proton exchange with H-resin and subsequent freeze-drying. The most crucial factor to isolate KH3[PMo11NbO40] and H4[PMo11NbO40] in pure forms is the evaporation of water using the freeze-drying method. Using a similar procedure, the potassium salt of the di-Nb substituted compound K5[PMo10Nb2O40] was isolated. H4[PMo11NbO40] exhibited high catalytic activity for oxidizing isobutylaldehyde to methacrolein and moderate catalytic activity for the Wacker-type oxidation of allyl phenyl ether when combined with Pd(OAc)2.

Preparation of α1- and α2-isomers of mono-Ru-substituted Dawson-type phosphotungstates with an aqua ligand and comparison of their redox potentials, catalytic activities, and thermal stabilities with Keggin-type derivatives.

Both the α1- and the α2-isomers of mono-ruthenium (Ru)-substituted Dawson-type phosphotungstates with terminal aqua ligands, [α1-P2W17O61Ru(III)(H2O)](7-) (α1-RuH2O) and [α2-P2W17O61Ru(III)(H2O)](7-) (α2-RuH2O), were prepared in pure form by cleavage of the Ru-S bond of the corresponding DMSO derivatives, [α1-P2W17O61Ru(DMSO)](8-) (α1-RuDMSO) and [α2-P2W17O61Ru(DMSO)](8-) (α2-RuDMSO), respectively. Redox studies indicated that α1-RuH2O and α2-RuH2O show proton-coupled electron transfer (PCET), and the Ru(III)(H2O) species was reversibly reduced to Ru(II)(H2O) species and oxidized to Ru(IV)([double bond, length as m-dash]O) species and further to Ru(V)([double bond, length as m-dash]O) species in aqueous solution depending on the pH. Their redox potentials and thermal stabilities were compared with those of the corresponding α-Keggin-type derivatives ([α-XW11O39Ru(H2O)](n-); X = Si(4+) (n = 5), Ge(4+) (n = 5), or P(5+) (n = 4)). The basic electronic and redox features of Ru(L)-substituted Keggin- and Dawson-type heteropolytungstates (with L = H2O or O(2-)) were analyzed by means of density functional calculations. Similar to the corresponding α-Keggin-type derivatives, both α1-RuH2O and α2-RuH2O show catalytic activity for water oxidation.