Francisco Pérez-Pla

Improving epoxide production using Ti-UVM-7 porous nanosized catalysts

Nanosized Ti-UVM-7 materials with a hierarchical system of pores at two different length scales have been prepared through a one-pot procedure by using a simple template agent; the catalytic activity and selectivity of the resulting materials in bulky olefin epoxidation by organic peroxides are the highest reported to date.

The reduction of tris-dithiolene complexes of molybdenum(VI) and tungsten(VI) by hydroxide ion: kinetics and mechanism

The kinetic study of the spontaneous reduction of some neutral tris-dithiolene complexes [ML3] of molybdenum(VI) and tungsten(VI), (L = S2C6H4(2-), S2C6H3CH3(2-) and S2C2(CH3)2(2-); M = Mo or W) by tetrabutylammonium hydroxide in tetrahydrofuran-water solutions demonstrates that OH- is an effective reductant. Their reduction is fast, clean and quantitative. Depending upon both the molar ratio in which the reagents are mixed and the amount of water present, one- or two-electron reductions of these tris-dithiolene complexes were observed. If Bu4NOH is present in low concentration or/and at high concentrations of water, the total transformation of the neutral M(VI) complex into the monoanionic M(V) complex is the only observed process. Stopped-flow kinetic data for this reaction are consistent with the rate law: -d[ML3]/dt = d[ML3-]/dt = k[ML3][Bu4NOH]. The proposed mechanism involves nucleophilic attack of OH- to form a mono-anionic seven-coordinate intermediate [ML3OH]-, which interacts with another molecule of [ML3] to generate the monoanionic complex [ML3]- transfering the oxygen from coordinated OH- to water. Hydrogen peroxide was identified as the reaction product. The molybdenum complexes are more difficult to reduce than their corresponding tungsten complexes, and the values of k obtained for the molybdenum and tungsten series of complexes increase as the ene-1,2-dithiolate ligand becomes more electron-withdrawing (S2C6H4(2-) > S2C6H3CH3(2-) > S2C2(CH3)2(2-)). This investigation constitutes the only well-established interaction between hydroxide ion and a tris(dithiolene) complex, and supports a highly covalent bonding interaction between the metal and the hydroxide ion that modulates electron transfer reactions within these complexes.

Towards the design of organocatalysts for nerve agents remediation: The case of the active hydrolysis of DCNP (a Tabun mimic) catalyzed by simple amine-containing derivatives.

We report herein a study of the hydrolysis of Tabun mimic DCNP in the presence of different amines, aminoalcohols and glycols as potential suitable organocatalysts for DCNP degradation. Experiments were performed in CD3CN in the presence of 5% D2O, which is a suitable solvent mixture to follow the DCNP hydrolysis. These studies allowed the definition of different DCNP depletion paths, resulting in the formation of diethylphosphoric acid, tetraethylpyrophosphate and phosphoramide species as final products. Without organocatalysts, DCNP hydrolysis occurred mainly via an autocatalysis path. Addition of tertiary amines in sub-stoichiometric amounts largely enhanced DCNP depletion whereas non-tertiary polyamines reacted even faster. Glycols induced very slight increment in the DCNP hydrolysis, whereas DCNP hydrolysis increased sharply in the presence of certain aminoalcohols especially, 2-(2-aminoethylamino)ethanol. For the latter compound, DCNP depletion occurred ca. 80-fold faster than in the absence of organocatalysts. The kinetic studies revealed that DCNP hydrolysis in the presence of 2-(2-aminoethylamino)ethanol occurred via a catalytic process, in which the aminoalcohol was involved. DCNP hydrolysis generally depended strongly on the structure of the amine, and it was found that the presence of the OHCH2CH2N moiety in the organocatalyst structure seems important to induce a fast degradation of DCNP.

Layered-Expanded Mesostructured Silicas: Generalized Synthesis and Functionalization

Mesostructured layered silicas have been prepared through a surfactant-assisted procedure using neutral alkylamines as templates and starting from atrane complexes as hydrolytic inorganic precursors. By adjusting the synthetic parameters, this kinetically controlled reproducible one-pot method allows for obtaining both pure and functionalized (inorganic or organically) lamellar silica frameworks. These are easily deconstructed and built up again, which provides a simple way for expanding the interlamellar space. The materials present high dispersibility, which results in stable colloidal suspensions.

Colloidally Confined Crystallization of Highly Efficient Ammonium Phosphomolybdate Catalysts

Nanodroplets in inverse miniemulsions provide a colloidal confinement for the crystallization of ammonium phosphomolybdate (APM), influencing the resulting particle size. The effects of the space confinement are investigated by comparing the crystallization of analogous materials both in miniemulsion and in bulk solution. Both routes result in particles with a rhombododecahedral morphology, but the ones produced in miniemulsion have sizes between 40 and 90 nm, 3 orders of magnitude smaller than the ones obtained in bulk solution. The catalytic activity of the materials is studied by taking the epoxidation of cis-cyclooctene as a model reaction. The miniemulsion route yields APM particles catalytically much more active than analogous samples produced in bulk solution, which can be explained by their higher dispersibility in organic solvents, their higher surface area, and their higher porosity. Inorganic phosphate salt precursors are compared with organic phosphate sources. APM nanoparticles prepared in miniemulsion from d-glucose-6-phosphate and O-phospho-dl-serine yield a conversion in the epoxidation reaction of more than 90% after only 1 h, compared to 30% for materials prepared in bulk solution. In addition, the catalysts prepared in miniemulsion display a promising recyclability.

Zirconium oxocluster/polymer hybrid nanoparticles prepared by photoactivated miniemulsion copolymerization

The photoactivated free radical miniemulsion copolymerization of methyl methacrylate (MMA) and the zirconium oxocluster Zr4O2(methacrylate)12 is used as an effective and fast preparation method for polymer/inorganic hybrid nanoparticles. The oxoclusters, covalently anchored to the polymer network, act as metal-organic cross-linkers, thus improving the thermomechanical properties of the resulting hybrid nanoparticles. Benzoin carbonyl organic compounds were used as photoinitiators. The obtained materials are compared in terms of cross-linking, effectiveness of cluster incorporation, and size distribution with the analogous nanoparticles produced by using conventional thermally induced free radical miniemulsion copolymerization. The kinetics of the polymerization process in the absence and in the presence of the oxocluster is also investigated.

Reduction of tris(benzene-1,2-dithiolate)molybdenum(VI) by hydroxide ions in dry tetrahydrofuran solution

Tris(benzene-1,2-dithiolate)molybdenum(VI) reacts rapidly and quantitatively with tetrabutylammonium hydroxide to yield the corresponding Mo(V) and Mo(IV) complexes and hydrogen peroxide; the reaction has been executed in dry tetrahydrofuran where the reaction rate shows a fair dependence on complex and OH- concentrations.