共查询到20条相似文献,搜索用时 15 毫秒
1.
A. J. Pardey M. Fernández M. Canestrari P. Baricelli E. Lujano C. Longo R. Sartori S. A. Moya 《Reaction Kinetics and Catalysis Letters》1999,67(2):325-331
Catalysts for the water gas shift reaction prepared from Rh(COD)(amine)2 PF6 (COD=1,5-cyclooctadiene, amine=4-picoline, 3-picoline, 2-picoline, pyridine, 3,5-lutidine or 2,6-lutidine) immobilized on
poly(4-vinylpyridine) in contact with 80% aqueoux 2-ethoxyethanol for 1×10−4 mol Rh/0.5 g of polymer, P(CO)=0.9 atm at 100 °C, are described. The role of the coordinated amine effect on the catalytic
activity was investigated. 相似文献
2.
A. J. Pardey M. Fernández M. A. Moreno J. Alvarez A. B. Rivas M. C. Ortega B. Mendez P. J. Baricelli C. Longo 《Reaction Kinetics and Catalysis Letters》2000,70(2):293-301
Homogeneous catalysts for the water gas shift reaction prepared from Rh2(-Pz)2(COD)2 (Pz = pyrazolate ion and COD = 1,5-cyclooctadiene) in aqueous organic solvent media (pyridine, 4-picoline or 2-ethoxyethanol) and Rh2(-Pz)2(CO)2(TPPMS)2 (TPPMS = meta-sulfonatophenyl-diphenyldiphosphine) in acidic aqueous media under mild conditions are described. In situ FT-IR, 1H and 13C NMR spectroscopic studies of the Rh2(-Pz)2(COD)2 catalytic system reveal the presence of hydrido-Rh complexes with linear and bridging carbonyls. These complexes also catalyze the reduction of nitrobenzene to aniline. 相似文献
3.
Fernando Hung-Low Gabriela C. Uzcátegui Juan Alvarez Marisol C. Ortega Alvaro J. Pardey Clementina Longo 《Reaction Kinetics and Catalysis Letters》2005,84(1):87-92
Summary Rhodium(I) complexes, [Rh(COD)(amine)2](PF6) (COD = 1,5-cyclooctadiene, amine = 4-picoline, 3-picoline, 2-picoline, pyridine, 3,5-lutidine or 2,6-lutidine) immobilized on poly(4-vinylpyridine) in contact with water catalyzed both the hydroxycarbonylation of 1-hexene to propionic acid and the water-gas shift reaction (WGSR). The role of the coordinated amine on the catalytic activity was examined. 相似文献
4.
Alvaro J. Pardey Fernando Hung-Low Gabriela C. Uzcátegui Marisol C. Ortega Clementina Longo 《Reaction Kinetics and Catalysis Letters》2006,88(2):203-208
Summary In this work, a mechanistic study of the hydroxycarbonylation of 1-hexene to heptanoic acid and the water gas shift reaction
(WGSR) catalyzed by the rhodium(I) complexes, [Rh(COD)(amine)2](PF6) (COD = 1,5-cyclooctadiene, amine = 4-picoline, 3-picoline, 2-picoline, pyridine, 3,5-lutidine or 2,6-lutidine) immobilized
on poly(4-vinylpyridine) in contact with water under CO is discussed. Catalytic cycles for these reactions bearing common
Rh-H catalytic species are proposed. 相似文献
5.
Alvaro J. Pardey José Brito María Fernández Angel B. Rivas Marisol C. Ortega Clementina Longo Pablo J. Baricelli Eduardo Lujano Sergio A. Moya 《Reaction Kinetics and Catalysis Letters》2001,74(1):111-118
Reported here is the influence of the reaction conditions variation (1-hexene/rhodium content (S/C) = 16 - 105, temperature (T) = 70 - 110 °C and carbon monoxide pressure (P(CO)) = 0.6 - 1.8 atm) on the catalytic hydroformylation of 1-hexene to aldehydes (heptanal and 2-methyl-hexanal) by the rhodium(I)
complex, [Rh(COD)(2-picoline)2]PF6 (COD = 1,5-cyclooctadiene)immobilized on poly(4-vinylpyridine) in contact with 10 mL of 80% aqueous 2-ethoxyethanol, under
water gas shift reaction condition.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
6.
《Polyhedron》2001,20(15-16):2089-2093
The reaction of [Ir(COD)Cl]2 with 2-(arylazo)pyridine (L) in dichloromethane solution has afforded the nonelectrolytic pentacoordinated species of type Ir(L)(COD)(Cl) from which the corresponding bromides and iodides have been synthesised by metathesis (COD=1,5-cyclooctadiene). L ligands used are: 2-(phenylazo)pyridine (L1); 2-(m-tolylazo)pyridine (L2) and 2-(p-chlorophenylazo)pyridine (L3). The X-ray structures of Ir(L2)(COD)(Cl)·0.5 CH2Cl2 and Ir(L3)(COD)(I) have been determined revealing square-pyramidal geometry. The relatively short IrN(azo) lengths (∼2.00 Å) and the relatively long NN bond distance (∼1.30 Å) are consistent with significant dππ* (azo) back-bonding. The HOMO (50% Ir and 15% azo character) and LUMO (50% azo and 30% Ir character) are primarily localised in the IrL fragment and the absorption bands near 600 nm is assigned tentatively to the HOMO→LUMO transition. The stability of the pentacoordinated structures and the inertness to oxidative addition of the present complexes in contrast to the behaviour of corresponding 2,2′-bipyridine species (tetracoordinated, reactive) is rationalised in terms of π-acidity order L≫bpy. 相似文献
7.
Qiaowen Chang Changyi Hu Jialin Chen Mingjin Xie Weiping Liu Qingsong Ye Yao Yu Xizhu Chen Liqiao Chen 《Transition Metal Chemistry》2011,36(4):337-340
A series of mixed-ligand complexes of tris(acetylacetonato) iridium(III) with N-heterocyclic ligands, namely [bis(acac-O,O′)(acac-C3)Ir(L)], where acac = acetyacetonato; L = 2-picoline (1), 3-picoline (2), 4-picoline (3), have been synthesized via the reaction
of [bis(acac-O,O′) (acac-C3)Ir(H2O)] with the corresponding ligand, respectively. Molecular structures of all complexes were determined by using single-crystal
X-ray diffraction. The results reveal that these complexes have slightly distorted octahedral coordination geometries. 相似文献
8.
Complexes of phenyl tin trichloride with bases as pyridine, β-picoline, γ-picoline, isoquinoline, piperidine, morpholine, aniline and benzylamine have been prepared. Their infrared spectra have been studied in the region 4000–250 cm?1 and molar conductance measurements carried out in nitrobenzene solutions. 相似文献
9.
S. A. Talipov M. T. Khonkeldieva L. Yu. Izotova Z. G. Tilyakov B. T. Ibragimov 《Journal of Structural Chemistry》2011,52(1):186-192
Gossypol forms stable solvates with 4- and 2-picolines at room temperature. The solvates are investigated by single crystal
X-ray diffraction and thermal analysis. Solvate crystals of gossypol with 4-picoline (1) have the 1:3 composition (gossypol:4-picoline) and crystallize in the P21/c space group. This substance is isostructural to a trisolvate of gossypol with pyridine. Solvate crystals of gossypol with
2-picoline (2) have the 1:4 composition (gossypol:2-picoline) and crystallize in the P-1 space group. The unit cell parameters for the investigated structures are as follows: 1 monoclinic crystals, C30H30O8·3C6H7N, a = 10.7530(1) ?, b = 20.7834(3) ?, c = 19.1166(2) ?, β = 95.537(1)°, V = 4252.32(9) ?3, M = 797.92, Z = 4, d
x = 1.246 g/cm3, and R = 0.0489 for 4102 reflections; 2 triclinic crystals, C30H30O8·4C6H7N, a = 11.467(1) ? b = 14.962(2) ?, c = 15.570(3) ?, α = 75.62(1)°, β = 69.83(1)°, γ = 79.58(1)°, V = 2414.6(7) ?3, M = 891.04, Z = 2, d
x = 1.226 g/cm3, and R = 0.0528 for 3779 reflections. The results of the single crystal XRD and thermal analysis confirm that gossypol with 4-picoline
forms a trisolvat, and a tetrasolvate with 2-picoline. The transition from 4-picoline to 2-picoline proves to change the type
of the host-guest association from one-dimensional to zero-dimensional, i.e., to lead to a new crystal structure. Desolvation
of compound 2 begins at a lower temperature than that for compound 1, which is explained by their different crystal structures. Keywords: gossypol, 4-picoline, 2-picoline, clathrate formation,
crystal structure. 相似文献
10.
Germán Gascón Marisol C. Ortega José D. Suárez Alvaro J. Pardey Clementina Longo 《Reaction Kinetics and Catalysis Letters》2008,94(1):85-89
Rhodium(I) complexes, cis-[Rh(CO)2(amine)2](PF6) (amine = 4-picoline, 3-picoline, 2-picoline, pyridine, 3,5-lutidine or 2,6-lutidine) dissolved in an aqueous solution of
tetrabutylammonium hydrogensulfate (N(C4H9)4HSO4), catalyze the water-gas shift reaction (WGSR). The role of the coordinated amine on the catalytic activity was examined. 相似文献
11.
S. M. Nabavizadeh 《Journal of the Iranian Chemical Society》2007,4(4):444-450
Complexation of osmium tetroxide (OsO4) with pyridine and its substituted derivatives (i.e. 4-picoline, 3 -picoline, 4-tertbutylpyridine, methyl nicotinate, 3,4-dimethylpyridine, 3-chloropyridine, and 3-phenylpyridine) has been studied at different temperatures in benzene. Spectrophotometric measurements have been carried out to obtain the equilibrium constants and thermodynamic parameters. The equilibrium constants of the resulting 1:1 complexes are found to vary in the order 3,4-Me2Py > 4-tBuPy > 4-MePy > 3-MePy > Py > 3- PhPy > 3-C(O)OMePy ≈ 3-ClPy. All complexes are enthalpy stabilized whereas the entropy changes counteract the complexation. The results are discussed in terms of different basicities of the substituted pyridines. 相似文献
12.
《Journal of Coordination Chemistry》2012,65(9):1555-1562
To understand the substituent effects of 3-picoline derivatives on reaction equilibrium, the interactions between a series of 3-picoline-like ligands and [OV(O2)2(D2O)]?/[OV(O2)2(HOD)]? in solution were explored by multinuclear (1H, 13C, and 51V) magnetic resonance, COSY, and HSQC in 0.15 mol L?1 NaCl ionic medium for mimicking physiological conditions. The relative reactivity among the 3-picoline derivatives is 3-methyl pyridine > nicotinate >nicotinamide > ethyl nicotinate. Competitive coordination results in the formation of a series of new six-coordinated peroxovanadate species [OV(O2)2L] n ? (L = 3-picoline derivatives, n = 1 or 2). Density functional calculations provide a reasonable explanation on the relative reactivity of the 3-picoline derivatives. Solvation effects play an important role in these reactions. 相似文献
13.
Modified catalytic system composed of selenium and cocatalysts such as pyridine and aniline, applied in the reduction of nitrobenzene
to aniline in the presence of carbon monoxide and water is described. The reaction proceeds at 150–200°C and 3–4 MPa gauge
pressure. After 1–2 h the reaction is complete, reaching nitrobenzene conversions of up to 98% with selectivity to aniline
near 100%. 相似文献
14.
Tris(acetylacetonato)ruthenium(III)(Ru(acac)3) was synthesized with RuCl3·nH2O and acetylacetone as raw materials. The structure of Ru(acac)3 was identified by FI-IR, 1H NMR, 13C NMR, and elemental analysis. It was used in the catalytic hydrogen transfer hydrogenation of nitrobenzene with sodium formate as hydrogen donor. The effects of reaction conditions on the process, such as temperature, time, dosage of catalyst, and kinds of hydrogen donor, were investigated. The optimal reaction parameters were determined as follows: 80 °C, 4.0 h, the substrate nitrobenzene 20 mL, sodium formate 27.20 g, Ru(acac)3 0.96 g, the conversion of nitrobenzene is 100.0 %, the yield of aniline and the selectivity to aniline are 96.65 %. The reaction mechanism is proposed and analyzed. It exhibited excellent catalytic properties in the hydrogen transfer hydrogenation of nitrobenzene to aniline. 相似文献
15.
New mixed ligand complexes of copper(II) dithiocarbamates of the general formula, [CuCl(R2dtc)L] or [CuCi(R′ dtc)L] (RCH3 or C2H5, R′ = (CH2)5, dtc =-NCSS? and L = Pyridine, 3-picoline or 4-picoline), have been prepared by the reaction of bis(dithiocarbamato)di-μ-chloro-dicopper(II) complexes with pyridine or picolines. The complexes are found to be non-electrolytes in nitrobenzene. Magnetic susceptibilities, i.r. and electronic spectra of the complexes are reported. A psuedo-tetrahedral structure is suggested for these complexes. 相似文献
16.
Mixed ligand complexes of NiII ion with 1-cyano-1-carboethoxyethylene-2,2-dithiolate (CED2−[S2C = C (CN)(COOC2H5)]2−) as a primary ligand and o-phenylenediamine (OPD), pyridine (py), α-picoline (α-pic), β-picoline (β-pic) or γ-picoline (γ-pic) as secondary ligands have been isolated and characterized on the basis of analytical data, molar
conductance, magnetic susceptibility, electronic and infrared spectral studies. The molar conductance data reveal that the
complexes have 1:1 electrolytic nature in DMF solution. Magnetic and electronic spectral studies suggest distorted octahedral
stereochemistry around NiII ion in its complexes. Infrared spectral studies suggest bidentate chelating behaviour of CED2− ion and OPD while other ligands show unidentate behaviour in their complexes. 相似文献
17.
The standard enthalpies and (in part) free energies and entropies of transfer from amine (L) to amine + diluent (D) mixtures have been determined for MX2L2 complexes at 25°C using chloroform, 1,1,2,2,-tetrachloroethane (TCE), benzene, chlorobenzene, and ethyl acetate as diluents (M=Co and Zn; X=Cl and Br; L = pyridine, -picoline, and -picoline). Thermodynamic functions of transfer indicate specific outer-sphere interactions of the complexes with amine and protic diluents (chloroform and TCE) and reveal solvent-solvent interactions of amine + protic diluent mixtures. The effects of the nature of X, L, and M of the MX2L2 complexes on their interaction with the components of the mixed solvent are discussed.Deceased. 相似文献
18.
CO activation in the [Ru(NH3)5CO]2+ ion has been demonstrated under nucleophilic conditions in pyridine or 2-ethoxyethanol solution at 100 °C. In the presence
of Me3NO the observed pseudo-first order rate constants were found to be sensitive only to auxiliary ligand concentration (pyridine
or methyl pyridines), but with a tendency towards rate saturation and the same limiting rate at large excess of each entering
ligand. A mechanism is proposed in which the rate-limiting step is viewed as an auxiliary ligand-assisted CO2 elimination, preceded by a fast reversible addition of Me3NO. This reaction pathway is also supported by the values determined for ΔH
‡ (81 ± 13 kJ mol−1) and ΔS
‡ (−114 ± 36 J mol−1 K−1).
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
19.
Shamim A. Chaudhri R. Ahmed M. Ejaz 《Journal of Radioanalytical and Nuclear Chemistry》1977,35(2):235-243
The extraction of HCl, HBr, HNO3, HClO4, H2SO4 and CH3COOH into solutions of 4-(5-nonyl)pyridine (NPy) and 2-hexylpyridine (HPy) dissolved in benzene has been studied. The results
show that the larger, less basic anions extract better (ClO
4
−
>CH3COO−≥NO
3
−
>Br−>Cl−>HSO
4
−
) due to their low aqueous hydration. The ionization constants of NPyH+ and HPyH+ as determined spectrophotometrically were found to be 5.97±0.06 and 5.94±0.05, respectively, at 25°C. 相似文献