Hydrocarbon oxidation catalyzed by iron and manganese porphyrins anchored on aminofunctionalized supports

The second-generation metalloporphyrins (MePs) [5,10,15,20-tetrakis(pentafluorophenyl)porphyrin iron(III)] chloride, FeP, and [5,10,15,20-tetrakis(pentafluorophenyl)porphyrin manganese(III)] chloride, MnP, were covalently attached to aminofunctionalized supports, with a view to preparing selective solid catalysts for the oxidation of organic compounds. Montmorillonite K10 functionalized with 3-aminopropyltriethoxysilane (Mont1) or modified with 3-chloropropyltriethoxysilane followed by reaction with 1,6-diaminohexane (Mont2), and silica gel functionalized with 3-aminopropyltriethoxysilane (Sil1) or modified with 3-chloropropyltriethoxysilane followed by reaction with 1,6-diaminohexane (Sil2) were synthesized and characterized by UV-Vis and IR spectroscopies, EPR, TGA, and X-ray diffractometry. The catalytic activities of the MePs immobilized on these supports were investigated for the oxidation of (Z)-cyclooctene, cyclohexane and styrene by PhIO or H2O2. The studied systems were efficient catalysts for the oxidation of all substrates, especially when PhIO was the oxidant. There was no MeP leaching from the supports, indicating that covalent binding is a very efficient method for catalyst immobilization. The immobilized FePs were more efficient catalysts than the corresponding MnPs, even when imidazole was employed as a cocatalyst for the supported MnPs. Although the yields of oxidized products obtained with H2O2 were lower than those achieved with PhIO, some heterogeneous MeP systems were more efficient than the parent MePs in solution, both in terms of product yield and selectivity.As metaloporfirinas de segunda geração (MePs), cloreto de [5,10,15,20-tetraquis(pentafluorofenil)porfirinaferro(III)], FeP, e cloreto de [5,10,15,20-tetraquis(pentafluorofenil)porfirinamanganês(III)], MnP, foram covalentemente ancoradas em suportes aminofuncionalizados, com o objetivo de preparar catalisadores sólidos seletivos para a oxidação de compostos orgânicos. Montmorillonita K10 funcionalizada com 3-aminopropiltrietoxissilano (Mont1) ou com 3-cloropropiltrietoxissilano seguida por reação com 1,6-diaminoexano (Mont2), e sílica gel funcionalizada com 3-aminopropiltrietoxissilano (Sil1) ou modificada com 3-cloropropiltrietoxissilano seguida por reação com 1,6-diaminoexano (Sil2) foram preparadas e caracterizadas por UV-Vis, IR, EPR, TGA e difratometria de raios X. As atividades catalíticas das MePs imobilizadas nestes suportes foram investigadas na oxidação de (Z)-cicloocteno, cicloexano e estireno por iodosilbenzeno (PhIO) ou H2O2. Os sistemas estudados foram catalisadores eficientes da oxidação de todos os substratos, especialmente utilizando PhIO como oxidante. Não se observou lixiviamento das MePs dos suportes, indicando que a ligação covalente é um método muito eficiente para a imobilização de catalisadores. As FePs imobilizadas foram catalisadores mais eficientes que as correspondentes MnPs, mesmo quando imidazol foi empregado como um co-catalisador para as MnPs ancoradas. Embora os rendimentos de produtos oxidados utilizando H2O2 tenham sido mais baixos que aqueles obtidos com PhIO, alguns sistemas heterogêneos envolvendo MePs foram mais eficientes que as correspondentes MePs em solução, tanto em termos de rendimento de produto quanto de seletividade.FAPESPCoordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES)CNP

Coordination Chemistry of the (eta(6)-p-Cymene)ruthenium(II) Fragment with Bis-, Tris-, andTetrakis(pyrazol-1-yl)borate Ligands: Synthesis, Structural, Electrochemical, and CatalyticDiastereoselective Nitroaldol Reaction Studies

Novel [Ru(eta(6)-p-cymene)(kappa(2)-L)X] and [Ru(eta(6)-p-cymene)(kappa(3)-L)]X center dot nH(2)O complexes (L = bis-, tris-, or tetrakis-pyrazolylborate; X = Cl, N-3, PF6, or CF3SO3) are prepared by treatment of [Ru(eta(6)-p-cymene)Cl-2](2) with poly-(pyrazolyl)borate derivatives [M(L)] (L in general; in detail L = Ph(2)Bp = diphenylbis-(pyrazol-1-yl)borate; L = Tp = hydrotris(pyrazol-1-yl)borate; L = pzTp = tetrakis(pyrazol-1-yl)borate; L = Tp(4Bo) = hydrotris(indazol-1-yl)borate, L = T-p4Bo,T-5Me = (5-methylindazol-1-yl)borate; L = Tp(Bn,4Ph) = hydrotris(3-benzyl-4-phenylpyrazol-1-yl)borate; M = Na, K, or TI) and characterized by analytical and spectral data (IR, ESIMS, H-1 and C-13 NMR). The structures of [Ru(eta(6)-p-cymene)(Ph(2)Bp)Cl] (1) and [Ru(eta(6)-p-cymene)(Tp)Cl] (3) have been established by single-crystal X-ray diffraction analysis. Electrochemical studies allowed comparing the electron-donor characters of Tp and related ligands and estimating the corresponding values of the Lever E-L ligand parameter. The complexes [Ru(eta(6)-p-cymene)-(kappa(2)-L)X] and [Ru(eta(6)-p-cymene)(kappa(3)-L)]X center dot nH(2)O act as catalyst precursors for the diastereoselective nitroaldol reaction of benzaldehyde and nitroethane to the corresponding beta-nitroalkanol (up to 82% yield, at room temperature) with diastereoselectivity toward the formation of the threo isomer

Complexes of copper(II) with 3-(ortho-substituted phenylhydrazo)pentane-2,4-diones: syntheses,properties and catalytic activity for cyclohexane oxidation

Reactions of copper(II) with 3-phenylhydrazopentane-2,4-diones X-2-C6H4-NHN = C{C(= O)CH3}(2) bearing a substituent in the ortho-position [X = OH (H2L1) 1, AsO3H2 (H3L2) 2, Cl (HL3) 3, SO3H (H2L4) 4, COOCH3 (HL5) 5, COOH (H2L6) 6, NO2 (HL7) 7 or H (HL8) 8] lead to a variety of complexes including the monomeric [CuL4(H2O)(2)]center dot H2O 10, [CuL4(H2O)(2)] 11 and [Cu(HL4)(2)(H2O)(4)] 12, the dimeric [Cu-2(H2O)(2)(mu-HL2)(2)] 9 and the polymeric [Cu(mu-L-6)](n)] 13 ones, often bearing two fused six-membered metallacycles. Complexes 10-12 can interconvert, depending on pH and temperature, whereas the Cu(II) reactions with 4 in the presence of cyanoguanidine or imidazole (im) afford the monomeric compound [Cu(H2O)(4){NCNC(NH2)(2)}(2)](HL4)(2)center dot 6H(2)O 14 and the heteroligand polymer [Cu(mu-L-4)(im)](n) 15, respectively. The compounds were characterized by single crystal X-ray diffraction (complexes), electrochemical and thermogravimetric studies, as well as elemental analysis, IR, H-1 and C-13 NMR spectroscopies (diones) and ESI-MS. The effects of the substituents in 1-8 on the HOMO-LUMO gap and the relative stability of the model compounds [Cu(OH)(L-8)(H2O)]center dot H2O, [Cu(L-1)(H2O)(2)]center dot H2O and [Cu(L-4)(H2O)(2)]center dot H2O are discussed on the basis of DFT calculations that show the stabilization follows the order: two fused 6-membered > two fused 6-membered/5-membered > one 6-membered metallacycles. Complexes 9, 10, 12 and 13 act as catalyst precursors for the peroxidative oxidation (with H2O2) of cyclohexane to cyclohexanol and cyclohexanone, in MeCN/H2O (total yields of ca. 20% with TONs up to 566), under mild conditions

Pyrazole or tris(pyrazolyl)ethanol oxo-vanadium(IV) complexes as homogeneous or supported catalysts for oxidation of cyclohexane under mild conditions

The oxovanadium(IV) complexes [VO(acac)(2)(Hpz)].HC(pz)(3) 1.HC(pz)(3) (acac= acetylacetonate, Hpz = pyrazole, pz = pyrazoly1) and [VOCl2{HOCH2C(pz)(3)}] 2 were obtained from reaction of [VO(acac)(2)] with hydrotris(1-pyrazolyl)methane or of VCl(3)with 2,2,2-tris(1-pyrazolyl)ethanol. The compounds were characterized by elemental analysis, IR, Far-IR and EPR spectroscopies, FAB or ESI mass-spectrometry and, for 1, by single crystal X-ray diffraction analysis. 1 and 2 exhibit catalytic activity for the oxidation of cyclohexane to the cyclohexanol and cyclohexanone mixture in homogeneous system (TONS up to 1100) under mild conditions (NCMe, 24h, room temperature) using benzoyl peroxide (BPO), tert-butyl hydroperoxide (TBHP), m-chloroperoxybenzoic acid (mCPBA), hydrogen peroxide or the urea-hydrogen peroxide adduct (UHP) as oxidants. 1 and 2 were also immobilized on a polydimethylsiloxane membrane (1-PDMS or 2-PDMS) and the systems acted as supported catalysts for the cyclohexane oxidation using the above oxidants (TONs up to 620). The best results were obtained with mCPBA or BP0 as oxidant. The effects of various parameters, such as the amount of catalyst, nitric acid, reaction time, type of oxidant and oxidant-to-catalyst molar ratio, were investigated, for both homogeneous and supported systems. (C) 2012 Elsevier B.V. All rights reserved

Preparation, characterization and catalytic studies of V2O5-SiO2 xerogel composite

In this work, we report the synthesis, characterization and catalytic properties of a vanadium oxide-silicon oxide composite xerogel prepared by a soft chemistry approach. In order to obtain such material, we submitted a vanadium pentoxide gel previously synthesized via protonation of metavanadate species to an ""in situ"" progressive polycondensation into silica gel. The material has been characterized by X-ray diffraction, infrared spectroscopy, thermogravimetric analysis and scanning electron microscopy. Further, the catalytic activity of this material was evaluated for the epoxidation of styrene and cyclooctene using iodosylbenzene, hydrogen peroxide and m-chloroperbenzoic acid as the oxidizing agent

Tetra-crowned porphyrin as P450 biomimetic model for carbamazepine oxidation

A substituted porphyrin bearing four crown ether units, H(2)(TCP), was synthesized from the reaction between (5,10,15,20-tetra(o-aminophenyl) porphyrin) and the acyl derivative of the ether (4-carboxy-18-crown-6). The free-base porphyrin was characterized by C, N, and H elemental analysis; UV-vis and IR spectroscopies; and (1)H NMR. The corresponding ironporphyrin, Fe(TCP)Cl, was obtained via iron insertion into H(2)(TCP). Fe(TCP)Cl was employed as catalyst for carbamazepine (CBZ) oxidation by iodosylbenzene (PhIO), 3-chloroperoxybenzoic acid (m-CPBA) or sodium hypochlorite (NaOCl), in methanol or in a biphasic water/dichloroethane system. The crowned ironporphyrin proved to be a highly efficient and selective catalyst for CBZ epoxidation even in the biphasic dichloroethane /H(2)O system, with no need for an additional phase transfer agent.FAPESPCNPqCAPE

Synthesis and Characterization of Semi-Interpenetrating Networks Based on Poly(dimethylsiloxane) and Poly(vinyl alcohol)

Semi-interpenetrating networks (Semi-IPNs) with different compositions were prepared from poly(dimethylsiloxane) (PDMS), tetraethylorthosilicate (TEOS), and poly (vinyl alcohol) (PVA) by the sol-gel process in this study. The characterization of the PDMS/PVA semi-IPN was carried out using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and swelling measurements. The presence of PVA domains dispersed in the PDMS network disrupted the network and allowed PDMS to crystallize, as observed by the crystallization and melting peaks in the DSC analyses. Because of the presence of hydrophilic (-OH) and hydrophobic (Si-(CH(3))(2)) domains, there was an appropriate hydrophylic/hydrophobic balance in the semi-IPNs prepared, which led to a maximum equilibrium water content of similar to 14 wt % without a loss in the ability to swell less polar solvents. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 115: 158-166, 2010FAPEMIGCNPqCAPE

Marked Stabilization of Redox States and Enhanced Catalytic Activity in Galactose Oxidase Models Based on Transition Metal <i>S</i>‑Methylisothiosemicarbazonates with −SR Group in Ortho Position to the Phenolic Oxygen

Reactions of 5-<i>tert</i>-butyl-2-hydroxy-3-methylsulfanylbenzaldehyde <i>S</i>-methylisothiosemicarbazone and 5-<i>tert</i>-butyl-2-hydroxy-3-phenylsulfanylbenzaldehyde <i>S</i>-methylisothiosemicarbazone with pentane-2,4-dione (Hacac) and triethyl orthoformate in the presence of M­(acac)₂ as template source at 107 °C afforded metal complexes of the type M^IIL¹ and M^IIL², where M = Ni and Cu, with a new Schiff base ligand with thiomethyl (H₂L¹) and/or thiophenyl (H₂L²) group in the ortho position of the phenolic moiety. Demetalation of NiL¹ in CHCl₃ with HCl­(g) afforded H₂L¹. The latter reacts with Zn­(OAc)₂·2H₂O with formation of ZnL¹. The effect of −SR groups and metal ion identity on stabilization of phenoxyl radicals generated electrochemically was studied in detail. A marked stabilization of phenoxyl radical was observed in one-electron-oxidized complexes [ML²]⁺ (M = Ni, Cu) at room temperature, as demonstrated by cyclic voltammetry, EPR spectroscopy, and UV–vis–NIR measurements. In solution, the oxidized CuL² and NiL² display intense low-energy NIR transitions consistent with their classification as metal-delocalized phenoxyl radical species. While the CuL² complex shows reversible reduction, reduction of NiL², CuL¹, and NiL¹ is irreversible. EPR measurements in conjunction with density functional theory calculations provided insights into the extent of electron delocalization as well as spin density in different redox states. The experimental room temperature spectroelectrochemical data can be reliably interpreted with the ³[CuL²]⁺ and ²[NiL²]⁺ oxidation ground states. The catalytic activity of synthesized complexes in the selective oxidations of alcohols has been studied as well. The remarkable efficiency is evident from the high yields of carbonyl products when employing both the CuL²/air/TEMPO and the CuL²/TBHP/MW­(microwave-assisted) oxidation systems

Marked Stabilization of Redox States and Enhanced Catalytic Activity in Galactose Oxidase Models Based on Transition Metal <i>S</i>‑Methylisothiosemicarbazonates with −SR Group in Ortho Position to the Phenolic Oxygen

Reactions of 5-<i>tert</i>-butyl-2-hydroxy-3-methylsulfanylbenzaldehyde <i>S</i>-methylisothiosemicarbazone and 5-<i>tert</i>-butyl-2-hydroxy-3-phenylsulfanylbenzaldehyde <i>S</i>-methylisothiosemicarbazone with pentane-2,4-dione (Hacac) and triethyl orthoformate in the presence of M­(acac)₂ as template source at 107 °C afforded metal complexes of the type M^IIL¹ and M^IIL², where M = Ni and Cu, with a new Schiff base ligand with thiomethyl (H₂L¹) and/or thiophenyl (H₂L²) group in the ortho position of the phenolic moiety. Demetalation of NiL¹ in CHCl₃ with HCl­(g) afforded H₂L¹. The latter reacts with Zn­(OAc)₂·2H₂O with formation of ZnL¹. The effect of −SR groups and metal ion identity on stabilization of phenoxyl radicals generated electrochemically was studied in detail. A marked stabilization of phenoxyl radical was observed in one-electron-oxidized complexes [ML²]⁺ (M = Ni, Cu) at room temperature, as demonstrated by cyclic voltammetry, EPR spectroscopy, and UV–vis–NIR measurements. In solution, the oxidized CuL² and NiL² display intense low-energy NIR transitions consistent with their classification as metal-delocalized phenoxyl radical species. While the CuL² complex shows reversible reduction, reduction of NiL², CuL¹, and NiL¹ is irreversible. EPR measurements in conjunction with density functional theory calculations provided insights into the extent of electron delocalization as well as spin density in different redox states. The experimental room temperature spectroelectrochemical data can be reliably interpreted with the ³[CuL²]⁺ and ²[NiL²]⁺ oxidation ground states. The catalytic activity of synthesized complexes in the selective oxidations of alcohols has been studied as well. The remarkable efficiency is evident from the high yields of carbonyl products when employing both the CuL²/air/TEMPO and the CuL²/TBHP/MW­(microwave-assisted) oxidation systems