Browsing by Author "Cunha-Silva, Luis"
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- A hydrogen-bonded assembly of cucurbit[6]uril and [MoO2Cl2(H2O)(2)] with catalytic efficacy for the one-pot conversion of olefins to alkoxy productsPublication . Nogueira, Lucie S.; Antunes, Margarida M.; Gomes, Ana C.; Cunha-Silva, Luis; Pillinger, Martyn; Lopes, Andre D.; Valente, Anabela A.; Goncalves, Isabel S.The reaction of the macrocyclic cavitand cucurbit[6]uril (CB[6]) and the diaqua complex [MoO2Cl2(H2O)(2)] in hydrochloric acid solution gave a water insoluble supramolecular compound with the general composition 2[MoO2Cl2(H2O)(2)]center dot CB[6]center dot xH(2)O center dot yHCl center dot z(CH3COCH3) (2). Single crystal X-ray diffraction (XRD) analysis revealed the presence of barrel-shape supramolecular entities, {CB[6]center dot 10(H2O)}, aligned in layers which are shifted relative to adjacent layers to form a brick-like pattern. The CB[6]/water hydrogen-bonded entities further engage in intermolecular interactions with water, HCl and [MoO2Cl2(H2O)(2)] molecules to form a three-dimensional (3D) framework. Compound 2 was characterised by thermogravimetric analysis (TGA), IR and Raman vibrational spectroscopy, and C-13{H-1} CP MAS NMR. The reference complex [MoO2Cl2(H2O)(2)]center dot(diglyme)(2) (1) and compound 2 were studied for the oxidative catalytic conversion of olefins (cis-cyclooctene, cyclohexene and styrene) with aqueous H2O2 as oxidant. Using alcohols as solvents, 2 was employed in a one-pot two-stage strategy for converting olefins to alkoxy products, which involves oxidation (with H2O2) and acid chemistry. Mechanistic studies were carried out using different intermediates as substrates, and the type of solvent and substrate scope were investigated. The results demonstrated the ability of the CB[6]/Mo-VI supramolecular adduct to function as an acid-oxidation multifunctional catalyst, and its recovery and reuse via relatively simple procedures.
- A silicododecamolybdate/pyridinium-tetrazole hybrid molecular salt as a catalyst for the epoxidation of bio-derived olefinsPublication . Nunes, Martinique S.; Neves, Patricia; Gomes, Ana C.; Cunha-Silva, Luis; Lopes, Andre D.; Valente, Anabela A.; Pillinger, Martyn; Goncalves, Isabel S.The hybrid polyoxometalate (POM) salt (Hptz)(4)[SiMo12O40].nH(2)O (1) (ptz = 5-(2-pyridyl)tetrazole) has been prepared, characterized by X-ray crystallography, and examined as a catalyst for the epoxidation of cis-cyclooctene (Cy) and bio-derived olefins, namely dl-limonene (Lim; a naturally occurring monoterpene found in the rinds of citrus fruits), methyl oleate and methyl linoleate (fatty acid methyl esters (FAMEs) obtained by transesterification of vegetable oils). The crystal structure of 1 consists of alpha-Keggin-type heteropolyanions, [SiMo12O40](4-), surrounded by space-filling and charge-balancing 2-(tetrazol-5-yl)pyridinium (Hptz(+)) cations, as well as by a large number of water molecules of crystallization (n = 9). The water molecules mediate an extensive three-dimensional (3D) hydrogen-bonding network involving the inorganic anions and organic cations. For the epoxidation of the model substrate Cy in a nonaqueous system (tert-butylhydroperoxide as oxidant), the catalytic performance of 1 (100% epoxide yield at 24 h, 70 degrees C) was superior to that of the tetrabutylammonium salt (Bu4N)(4) [SiMo12O40] (2) (63% epoxide yield at 24 h), illustrating the role of the counterion Hptz(+) in enhancing catalytic activity. The hybrid salt 1 was effective for the epoxidation of Lim (69%/85% conversion at 6 h/24 h) and the FAMEs (87-88%/100% conversion at 6 h/24 h), leading to useful bio-based products (epoxides, diepoxides and diol products).
- Dichlorodioxomolybdenum(VI) complexes bearing oxygen-donor ligands as catalysts for oxidative desulfurization of simulated and real dieselPublication . Juliao, Diana; Gomes, Ana C.; Cunha-Silva, Luis; Pillinger, Martyn; Lopes, Andre D.; Valenca, Rita; Ribeiro, Jorge C.; Goncalves, Isabel S.; Balula, Salete S.The complexes [MoO2Cl2(DMB)(2)] (1) and [MoO2Cl2(DEO)] (2) (DMB = N,N-dimethylbenzamide, DEO = N,N'-diethyloxamide) have been evaluated as catalysts in extractive-catalytic oxidative desulfurization (ECOD) of a simulated diesel fuel. Using the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6) as extraction solvent and H2O2 as oxidant, ultra-deep desulfurization (S-content from 3000 ppm to < 10 ppm) was possible within a reaction time of 1-3 h, and the systems Catalyst/[BMIM]PF6 could be recycled for five times without significant decrease in activity. The S-content of a real untreated diesel was lowered by 94.4% from 2300 ppm to 129 ppm after only 2 h of reaction using the ECOD process with 2 as catalyst.