Browsing by Author "Pillinger, Martyn"
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- A 5-(2-Pyridyl) tetrazolate complex of Molybdenum(VI), its structure, and transformation to a Molybdenum Oxide-Based Hybrid Heterogeneous Catalyst for the Epoxidation of OlefinsPublication . Nunes, Martinique S.; Gomes, Diana M.; Gomes, Ana C.; Neves, Patrícia; Mendes, Ricardo F.; Paz, Filipe A. Almeida; Lopes, A. D.; Valente, Anabela A.; Gonçalves, Isabel S.; Pillinger, MartynThere is a considerable practical interest in discovering new ways to obtain organomolybdenum heterogeneous catalysts for olefin epoxidation that are easier to recover and reuse and display enhanced productivity. In this study, the complex salt (H2pytz)[MoO2Cl2 (pytz)] (1) (Hpytz = 5-(2-pyridyl)tetrazole) has been prepared, structurally characterized, and employed as a precursor for the hydrolysis-based synthesis of a microcrystalline molybdenum oxide/organic hybrid material formulated as [MoO3 (Hpytz)] (2). In addition to single-crystal X-ray diffraction (for 1), compounds 1 and 2 were characterized by FT-IR and Raman spectroscopies, solid-state 13C{1H} cross-polarization (CP) magic-angle spinning (MAS) NMR, and scanning electron microscopy (SEM). Compounds 1 and 2 were evaluated as olefin epoxidation catalysts using the model reaction of cis-cyclooctene (Cy8) with tert-butyl hydroperoxide (TBHP), at 70 ◦C, which gave 100% epoxide selectivity up to 100% conversion. While 1 behaved as a homogeneous catalyst, hybrid 2 behaved as a heterogeneous catalyst and could be recovered for recycling without showing structural degradation or loss of catalytic performance over consecutive reaction cycles. The substrate scope was broadened to monoterpene DL-limonene (Lim) and biobased unsaturated fatty acid methyl esters, methyl oleate (MeOle), and methyl linoleate (MeLin), which gave predominantly epoxide products.
- 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).
- Bis(pyrazolyl)methanetetracarbonyl-molybdenum(0) as precursor to a molybdenum(VI) catalyst for olefin epoxidationPublication . Figueiredo, Sónia; Gomes, Ana C.; Fernandes, José A.; Paz, Filipe A. Almeida; Lopes, Andre D.; Lourenço, J. P.; Pillinger, Martyn; Gonçalves, Isabel S.Bis(pyrazolyl)methanetetracarbonyl-molybdenum(0), cis-[Mo(CO)4(BPM)] (1), was prepared from Mo(CO)6 and the ligand bis(pyrazolyl)methane (BPM), and examined as a catalyst precursor for the epoxidation of olefins using tert-butylhydroperoxide (TBHP) as oxidant. Catalytic activities followed the sequence 1-octene < trans-2-octene < a-pinene < (R)-(þ)-limonene < cis-cyclooctene, and, with the exception of a-pinene and limonene, the corresponding epoxide was always the only reaction product. Turnover frequencies for the epoxidation of cyclooctene were 580 mol molMo 1 h 1 at 55 C and 1175 mol molMo 1 h 1 at 75 C, which compare favourably with those found for other molybdenum carbonyl complexes used as catalyst precursors for the same reaction under similar conditions. Catalytic activities were lower in the presence of organic co-solvents, decreasing in the sequence 1,2-dichloroethane > nitromethane > ethanol > hexane > acetonitrile. It is proposed that the oxodiperoxo complex [MoO(O2)2(BPM)] (2) may be the active catalyst formed in situ by oxidative decarbonylation of 1, since crystals of 2 suitable for structure determination by X-ray diffraction were obtained from the reaction solution recovered after a catalytic run at 55 C with cis-cyclooctene as substrate. In support of this hypothesis, the catalytic performance of 2 for the epoxidation of cyclooctene at 55 C is very similar to that for 1.
- Catalytic alcoholysis of epoxides using metal-free cucurbituril-based solidsPublication . Bruno, Sofia M.; Gomes, Ana C.; Oliveira, Tânia S. M.; Antunes, Margarida M.; Lopes, Andre D.; Valente, Anabela A.; Gonçalves, Isabel S.; Pillinger, MartynMetal-free cucurbit[7]uril (CB7) solid-state assemblies promote acid-catalysed alcoholysis of aliphatic and aromatic epoxides under mild conditions to give beta-alkoxy alcohols, which are important intermediates for the synthesis of a vast range of compounds such as bioactive pharmaceuticals. The catalytic process is heterogeneous and the catalyst can be reused in consecutive runs without any reactivation treatment. The acid species responsible for the catalytic activity of CB7 may be entrapped hydronium ions.
- Catalytic epoxidation and sulfoxidation activity of a dioxomolybdenum(VI) complex bearing a chiral tetradentate oxazoline ligandPublication . Neves, Patrícia; Gago, Sandra; Pereira, Cláudia C. L.; Figueiredo, Sónia; Lemos, Americo; Lopes, Andre D.; Gonçalves, Isabel S.; Pillinger, Martyn; Silva, Carlos M.; Valente, Anabela A.A dioxomolybdenum(VI) complex bearing a tetradentate anionic N,O oxazoline ligand with four stereocenters has been studied as a catalyst in the liquid-phase epoxidation of 17 different aliphatic and aromatic olefins(including prochiral, racemate or pure enantiomers) using tert-butyl hydroperoxide as the oxidant. Epoxide selectivities of up to 100% and variable epoxide yields (3–100% within 24 h) were obtained. Although the complex generally exhibited low or no chiral induction ability, diastereoselectivity was significant in some cases (in the reaction of limonene, for example). Kinetic studies and recycling tests with the substrates cis-cyclooctene and trans-b-methylstyrene showed that the catalyst is stable and reusable, and recycling is facilitated by immobilization of the complex in a room temperature ionic liquid. Preliminary results show that the complex may have a broad substrate scope, not only for olefin epoxidation, but also for the dehydrogenation of alcohols to carbonyl compounds and the sulfoxidation of sulfides to sulfoxides.
- Chemistry and catalytic performance of pyridyl-benzimidazole oxidomolybdenum(VI) compounds in (bio)olefin epoxidationPublication . Neves, Patricia; Nogueira, Lucie S.; Gomes, Ana C.; Oliveira, Tânia S. M.; Lopes, Andre D.; Valente, Anabela A.; Gonçalves, Isabel S.; Pillinger, MartynThe chemistry and catalytic performance of the dichlorido complex [MoO2Cl2(pbim)] (1) [pbim = 2-(2-pyridyl)benzimidazole] in the epoxidation of olefins is reported. Complex 1 acts as a precatalyst and is more effective with tert-butyl-hydroperoxide (TBHP) as the oxidant than with aq. hydrogen peroxide: the cis-cyclooctene (Cy) reaction with TBHP gave 98 % epoxide yield at 70 degrees C/24 h. Catalyst characterization showed that 1 is transformed in situ to the oxidodiperoxido complex [MoO(O-2)(2)(pbim)] (2), with H2O2 and a hybrid molybdenum(VI) oxide solid formulated as [MoO3(pbim)] (3) with TBHP. The hybrid material 3 was prepared on a larger scale and explored for the epoxidation of the biorenewable olefins methyl oleate, methyl linoleate, and (R)-(+)-limonene. With TBHP as the oxidant, 3 acts as a source of soluble active species of the type 2. A practical method for recycling oxidodiperoxidomolybdenum(VI) catalysts for the Cy/TBHP reaction is demonstrated by using an ionic liquid as the solvent for the molecular catalyst 2.
- Comparison of liquid-phase olefin epoxidation catalysed by dichlorobis-(dimethylformamide)dioxomolybdenum(VI) in homogeneous phase and grafted onto MCM-41Publication . Monteiro, Bernardo; Balula, Salete S.; Gago, Sandra; Grosso, Carla; Figueiredo, Sónia; Lopes, Andre D.; Valente, Anabela A.; Pillinger, Martyn; Lourenço, J. P.; Gonçalves, Isabel S.A mesoporous silica-supported molybdenum oxide catalyst with a loading of 0.17Mo/nm2 was prepared by liquid phase deposition ofMoO2Cl2(dmf)2 (1) onto MCM-41 (dmf = dimethylformamide). Powder X-ray diffraction and N2 adsorption studies of Mo-MCM-41 indicate that the texture properties of the support were preserved during the grafting experiment. On the basis of evidence from FTIR spectroscopy, 13C and 29Si MAS NMR, and Mo K-edge EXAFS, the Mo atoms in this catalyst are mainly present as isolated {MoO2[(–O)3SiO]2(dmf)2} species, with a small contribution from oxo-bridged dimers. Catalysis tests show that complex 1 and Mo-MCM-41 are highly active oxidation catalysts for liquid-phase epoxidation of unfunctionalised olefins using tert-butylhydroperoxide as oxidant, from ambient to 55 ◦C. The high stability and recyclability of the heterogeneous Mo-MCM-41 catalyst is attributed to the strong metal oxide–support interaction. With cyclooctene, 1-octene, trans-2-octene and norbornene substrates, the corresponding epoxides were the only observed reaction products. The reactions of the other substrates gave by-products such as 8,9-p-menthen-1,2-diol from (R)-(+)-limonene, campholenic aldehyde from -pinene, and benzaldehyde from styrene. The addition of dichloromethane as a co-solvent had a beneficial effect on catalytic performance, and in the case of (R)-(+)-limonene allowed the epoxide to be formed as the only reaction product.
- Desulfurization of diesel by extraction coupled with Mo-catalyzed sulfoxidation in polyethylene glycol-based deep eutectic solventsPublication . Juliao, Diana; Gomes, Ana C.; Pillinger, Martyn; Lopes, Andre D.; Valenca, Rita; Ribeiro, Jorge C.; Goncalves, Isabel S.; Balula, Salete S.Oxidative desulfurization (ODS) is a method of removing sulfur from diesel fuel that has the potential to complement or even replace conventional hydrodesulfurization processes in oil refineries. One of the most promising variants of ODS is extractive and catalytic ODS (ECODS) in which the organic sulfur compounds in the liquid fuel are oxidized and extracted in situ from the oil phase into an extractant phase. In this study, the desulfurizalion of model and real diesel fuel has been performed in ECODS systems employing two different types of deep eutectic solvents (DESs), prepared by combining polyethylene glycol (PEG) as hydrogen bond donor with tetrabutylammonium chloride (TBACl) or choline chloride (ChCl) as hydrogen bond acceptor. The ECODS systems were evaluated with the complexes [MoO2Cl2(DMB)(2)] (1) and [MoO2Cl2(DEO)] (2) (DMB - N,N-dimethylbenzamide, DEO = N,N'-diethyloxamide) as catalysts and 30 wt% H2O2 as oxidant. The effects of different reaction conditions, such as the amount of catalyst, H2O2 and DES, and reaction temperature, were investigated. The combination of complex 1 with the DES ChCl/PEG showed the best performance for the removal of dibenzothiophene, 4-methyldibenzothiophene and 4,6-di methyldibenzothiophene from a high-sulfur (3000 ppm) model diesel, allowing a desulfurization efficiency of 99.6% to be attained at 70 degrees C within 2 h. By applying the optimized model diesel ECODS systems to the treatment of a commercial untreated diesel with a sulfur content of 2300 ppm. 82% of sulfur compounds could be eliminated. These promising results indicate that DESs are a viable alternative to ionic liquids as extraction solvents in ECODS processes. (C) 2020 Elsevier B.V. All rights reserved.
- Dichloro and dimethyl dioxomolybdenum(VI)–diazabutadiene complexes as catalysts for the epoxidation of olefinsPublication . Moreira, José; Valente, Anabela A.; Pillinger, Martyn; Nunes, Carla D.; Gonçalves, Isabel S.; Lopes, Andre D.; Romão, Carlos C.; Kuhn, Fritz E.The dioxomolybdenum(VI) complex [MoO2Cl2{p-tolyl(CH3DAB)}] has been prepared in good yield by reaction of the solvent adduct MoO2Cl2(THF)2 with one equivalent of the bidentate ligand N,N-p-tolyl-2,3-dimethyl- 1,4-diazabutadiene. Treatment of the dichloro complex with the Grignard reagent CH3MgCl gives the dimethyl derivative [MoO2(CH3)2{p-tolyl(CH3DAB)}]. The complexes are highly active and selective catalysts for the homogeneous epoxidation of cyclooctene using tert-butyl hydroperoxide (TBHP) as the oxidant. In both cases, the initial activity is ca. 175 mol mol 1 Mo h 1 and cyclooctene oxide is obtained quantitatively within 4 h. It was possible to recover the dimethyl complex at the end of the reaction and reuse it in a second run with only a small decrease in activity. The complexes are also active and selective for the epoxidation of other olefins, such as 1-octene, 2-octene, cyclododecene and (R)-(þ)-limonene, with TBHP. The catalytic production of cyclooctene oxide was investigated in detail, varying either the reaction temperature or the initial concentrations of substrate, oxidant and catalyst precursor. Kinetic studies show that the catalyst precursor–oxygen donor complex formation is first-order in TBHP and in the metal complex [MoO2Cl2{p-tolyl(CH3DAB)}]. A specific rate of 3.2 mol 1 dm3 s 1 was found for catalyst formation at 25 C. Activation parameters for this reaction have also been measured (DH6¼ ¼ 48 3 kJ mol 1, DS6¼ ¼ 112 10 J mol 1 K 1).