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- Heterogenisation of a c-scorpionate feII complex on carbon materials for cyclohexane oxidation with hydrogen peroxidePublication . Martins, Luisa; Almeida, M. Peixoto de; Carabineiro, S. A. C.; Figueiredo, J. L.; Pombeiro, ArmandoThe hydrotris(pyrazol-1-yl)methane iron(II) complex [FeCl2{h3-HC(pz)3}] (pz=pyrazol-1-yl) (1) was immobilized on three diferente carbon materials (activated carbon, carbon xerogel and multi-walled carbon nanotubes) with three different surface treatments (original, treated with nitric acid, and treated with nitric acid followed by sodium hydroxide) to produce active, selective and recyclable catalysts. The heterogenisation process was more efficient for carbon nanotubes treated with nitric acid and sodium hydroxide. An outstanding improved catalytic performance of complex 1 upon heterogenisation on carbon nanotubes treated with nitric acid and sodium hydroxide (turnover numbers up to 5.6_103 and overall yield of 21 %), relative to the homogeneous system, was achieved for the single-pot peroxidative oxidation of cyclohexane to the cyclohexanone and cyclohexanol mixture. The heterogenised systems allowed their easy recovery and reuse, at least for five consecutive cycles, maintaining 96% of the initial activity and concomitante rather high selectivity to cyclohexanol and cyclohexanone.
- New trendy magnetic C-scorpionate iron catalyst and its performance towards cyclohexane oxidationPublication . Da Costa Ribeiro, Ana Paula; Matias, Inês; Alegria, Elisabete; Ferraria, Ana Maria; Rego, Ana; Pombeiro, Armando; Martins, LuisaFor the first time, a magnetic C-scorpionate catalyst was prepared from the iron(II) complex [FeCl2{_3-HC(pz)3}] (pz = pyrazol-1-yl) and ferrite, using the sustainable mechanochemical synthetic procedure. Its catalytic activity for the cyclohexane oxidation with tert-butyl hydroperoxide (TBHP) was evaluated in different conditions, namely under microwave irradiation and under the effect of an external magnetic field. The use of such magnetic conditions significantly shifted the catalyst alcohol/ketone selectivity, thus revealing a promising, easy new protocol for tuning selectivity in important catalytic processes.
- Synthesis and structural characterization of iron complexes with 2,2,2-tris(1-pyrazolyl)ethanol ligands: Application in the peroxidative oxidation of cyclohexane under mild conditionsPublication . Silva, Telma F. S.; Guedes Da Silva, M. Fátima C.; Mishra, Gopal; Martins, Luisa; Pombeiro, ArmandoThe reactions of FeCl2 center dot 2H(2)O and 2,2,2-tris(1-pyrazolyl) ethanol HOCH2C(pz)(3) (1) (pz = pyrazolyl) afford [Fe{HOCH2C(pz)(3)}(2)][FeCl4]Cl (2), [Fe{HOCH2C(pz)(3)}(2)](2)[Fe2OCl6](Cl)(2)center dot 4H(2)O (3 center dot 4H(2)O), [Fe{HOCH2C(pz)(3)}(2)] [FeCl{HOCH2C(pz)(3)}(H2O)(2)](2)(Cl)(4) (4) or [Fe{HOCH2C(pz)(3)}(2)]Cl-2 (5), depending on the experimental conditions. Compounds 1-5 were isolated as air-stable crystalline solids and fully characterized, including (1-4) by single-crystal X-ray diffraction analyses. The latter technique revealed strong intermolecular H-bonds involving the OH group of the scorpionate 2 and 3 giving rise to 1D chains which, in 3, are further expanded to a 2D network with intercalated infinite and almost plane chains of H-interacting water molecules. In 4, intermolecular pi center dot center dot center dot pi interactions involving the pyrazolyl rings are relevant. Complexes 2-5 display a high solubility in water (S-25 degrees C ca. 10-12 mg mL(-1)), a favourable feature towards their application as catalysts (or catalyst precursors) for the peroxidative oxidation of cyclo-hexane to cyclohexanol and cyclohexanone, with aqueous H2O2/MeCN, at room temperature (TON values up to ca. 385). (C) 2011 Elsevier B. V. All rights reserved.
- Liquid phase oxidation of xylenes catalyzed by the tripodal C-scorpionate iron(II) complex [FeCl2{κ3-HC(pz)(3)}]Publication . Mendes, Marta; Da Costa Ribeiro, Ana Paula; Alegria, Elisabete; Martins, Luisa; Pombeiro, ArmandoA simple and mild (room temperature) process for oxidation of o-, m- or p-xylene to the corresponding methylbenzyl alcohols, tolualdehydes and toluic acids, using H2O2 (30% aqueous solution) and the iron(II) C-scorpionate [FeCl2{κ3-HC(pz)3}] (pz = pyrazol-1-yl) catalyst is presented. Remarkably, after 5 min of reaction an overall oxygenates yield of 22% (TOF = 1.3 × 102 h−1) was obtained. The effects of reaction parameters, such as reaction time, temperature, amount of catalyst, type and amount of oxidant are reported and discussed.
- Half‐sandwich scorpionate vanadium, iron and copper complexes: synthesis and application in the catalytic peroxidative oxidation of cyclohexane under mild conditionsPublication . Silva, Telma F. S.; Alegria, Elisabete; Martins, Luisa; Pombeiro, ArmandoThe new half‐sandwich scorpionate complexes [hydridotris(1‐pyrazolyl)methane]vanadium trichloride, ([VCl3{HC(pz)3}] 1 (pz=pyrazolyl), [tris(1‐pyrazolyl)methanesulfonate]vanadium trichloride, [VCl3{SO3C(pz)3}] 2 , [hydrido(1‐pyrazolyl)methane]iron dichloride, [FeCl2{HC(pz)3}] 3 , lithium [tris(1‐pyrazolyl)methanesulfonate]dichloroferrate, Li[FeCl2{SO3C(pz)3}] 4 , and [tris(1‐pyrazolyl)methanesulfonate]copper chloride, [CuCl{SO3C(pz)3}] 5 were synthesized, characterized and shown to act, as well as the related (tripyrazolylmethane)copper dichloride, [CuCl2{HC(pz)3}] 6 , as selective catalysts (or catalyst precursors) for the peroxidative oxidation (with hydrogen peroxide) of cyclohexane to cyclohexanol and cyclohexanone, under mild conditions (at room temperature and using an aqueous solution of H2O2). The iron complexes are the most active ones (reaching TON values up to ca. 690), the effects of a variety of factors are reported and the reaction is shown to proceed via both C‐ and O‐centred radical mechanisms, conceivably involving a metal‐based oxidant.
- C-scorpionate iron(II) complexes as highly selective catalysts for the hydrocarboxylation of cyclohexanePublication . Matias, Inês; Da Costa Ribeiro, Ana Paula; Alegria, Elisabete; Pombeiro, Armando; Martins, LuisaThe C-scorpionate iron(II) complexes [FeCl2{kappa(3)-HC(pz)(3)}](1) (pz = pyrazol-1-yl), Li[FeCl2{kappa(3)-SO3C(pz)(3)}] (2) and the new [FeCl2{kappa(3)-HOCH2C(pz)(3)}] (3) act as catalysts for the hydrocarboxylation of cyclohexane (with CO and H2O) to cyclohexanecarboxylic acid in a remarkable yield (up to 60%) and under mild conditions. The catalysts selectivity for the acid can be tuned by CO pressure, catalyst amount and reaction temperature. Complex [FeCl2{kappa(3)-HC(pz)(3)}] (1) provides the most effective catalyst requiring low CO pressure. This work constitutes an unprecedented use of iron complexes as catalysts for the hydrocarboxylation of alkanes.
- Fe@Hierarchical BEA zeolite catalyst for MW-assisted alcohol oxidation reaction: a greener approachPublication . Andrade, Marta A.; Ansari, Leonardo M. S.; Pombeiro, Armando; Carvalho, Ana P.; Martins, Angela; Martins, LuisaThe aim of this study was to investigate the catalytic activity of hybrid materials of iron supported on hierarchical zeolites in the oxidation reaction of 1-phenylethanol to acetophenone. A greener approach was considered for the preparation of the catalyst and performance of the oxidation reaction. Hierarchical BEA zeolite samples were obtained from an alkaline and a subsequent acid treatment. The materials were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and nitrogen adsorption at -196 degrees C. An iron salt was incorporated onto the hierarchical zeolites by mechanochemical grinding and the catalytic performance of the prepared materials was evaluated towards the microwave assisted oxidation reaction of 1-phenylethanol. The catalyst obtained by Fe immobilization on sample modified by 0.2 M NaOH followed by acid treatment (Fe@BEA0.2AT) is the most promising material with 35% yield and 56% selectivity to acetophenone, allowing five reuse cycles without significant loss of activity and selectivity.