Discovery of a Neutral 40-Pd-Oxo Molecular Disk, [PdO(OH){(CH)AsO}]: Synthesis, Structural Characterization, and Catalytic Studies.

We report on the synthesis and structural characterization of a giant, discrete, and neutral molecular disk, [PdO(OH){(CH)AsO}] (), comprising a 40-palladium-oxo core that is capped by 16 dimethylarsinate moieties, resulting in a palladium-oxo cluster (POC) with a diameter of ∼2 nm. , which is the largest known neutral Pd-based oxo cluster, can be isolated either as a discrete species or constituting a 3D H-bonded organic-inorganic framework (HOIF) with a 12-tungstate Keggin ion, [SiWO] or [GeWO]. H and C NMR as well as H-DOSY NMR studies indicate that is stable in aqueous solution, which is also confirmed by ESI-MS studies.

Discrete Polyoxopalladates as Molecular Precursors for Supported Palladium Metal Nanoparticles as Hydrogenation Catalysts.

We have used discrete polyoxopalladates(II) (POPs) of the MPdX nanocube- and PdX nanostar-types (M = central metal ion, X = capping group) as molecular precursors (diameter ca. 1 nm) for the formation of supported (SBA-15) metallic nanoparticles. These materials proved to be highly active in the hydrogenation of o-xylene.

Organo-ruthenium supported heteropolytungstates: synthesis, structure, electrochemistry, and oxidation catalysis.

The reaction of [Ru(arene)Cl(2)](2) (arene = benzene, p-cymene) with [X(2)W(22)O(74)(OH)(2)](12-) (X = Sb(III), Bi(III)) in buffer medium resulted in four organo-ruthenium supported heteropolytungstates, [Sb(2)W(20)O(70)(RuC(6)H(6))(2)](10-) (1), [Bi(2)W(20)O(70)(RuC(6)H(6))(2)](10-) (2), [Sb(2)W(20)O(70)(RuC(10)H(14))(2)](10-) (3), and [Bi(2)W(20)O(70)(RuC(10)H(14))(2)](10-) (4), which have been characterized in solution by multinuclear ((183)W, (13)C, (1)H) NMR, UV-vis spectroscopy, electrochemistry, and in the solid state by single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and elemental analysis. Polyanions 1, 2, and 4 crystallize in the triclinic system, space group P1 with the following unit cell parameters: K(5)Na(5)[Sb(2)W(20)O(70)(RuC(6)H(6))(2)] x 22 H(2)O (KNa-1), a = 12.1625(2) A, b = 13.

Heterogeneous wheel-shaped Cu20-polyoxotungstate [Cu20Cl(OH)24(H2O)12(P8W48O184)]25- catalyst for solvent-free aerobic oxidation of n-hexadecane.

The selective oxidation of alkanes as a green process remains a challenging task because partial oxidation is easier to achieve with sacrificial oxidants, such as hydrogen peroxide, alkyl hydroperoxides or iodosylbenzene, than with molecular oxygen or air. Here, we report on a heterogeneous catalyst for n-hexadecane oxidation comprised of the wheel shaped Cu20-polyoxotungstate [Cu20Cl(OH)24(H2O)12(P8W48O184)]25- anchored on 3-aminopropyltriethoxysilane (apts)-modified SBA-15. The catalysts were characterized by powder X-ray diffraction (XRD), N2-adsorption measurements and Fourier transform infrared reflectance (FT-IR) spectroscopy.

Solvent-free aerobic oxidation of n-alkane by iron(III)-substituted polyoxotungstates immobilized on SBA-15.

The tetrairon(III)-substituted polytungstates [Fe(4)(H(2)O)(10)(beta-XW(9)O(33))(2)](n-) (n = 6, X = As(III), Sb(III); n = 4, X = Se(IV), Te(IV)) were immobilized on (3-aminopropyl)triethoxysilane-modified SBA-15 and showed an excellent catalytic performance for solvent-free aerobic oxidation of long-chain n-alkanes using air as the oxidant under ambient conditions through a classical free-radical chain autoxidation mechanism.