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  • General Chemistry  (29)
  • Industrial Chemistry and Chemical Engineering  (7)
  • Wiley-Blackwell  (36)
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1547-1553 
    ISSN: 1434-1948
    Keywords: Imidazaboles ; Carbene-borane adducts ; Azole-borane adducts ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation and characterization of five new imidazabole derivatives is reported: 1,5-dibenzyl-4,4,8,8-tetrahydroimidazabole (2), 4,4,8,8-tetrafluoro-1,5-dimethylimidazabole (3), 4,4-difluoro-8,8-dihydro-1,5-dimethylimidazabole (4), 4,4,8,8-tetrachloro-1,5-dimethylimidazabole (5), and 4,4,8,8-tetraethyl-1,5-dimethylimidazabole (6). The structures of compounds 2-6 as dimeric carbene-borane adducts rather than dimeric N-borane adducts are discussed on the basis of NMR (2-6) and X-ray diffraction data (2, 3, 5 and 6).
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  • 2
    ISSN: 1434-1948
    Keywords: Alkaline earth metals ; Group-13 metals ; Coordination chemistry ; Bis(3,5-di-tert-butyl-1-hydroxy-2-phenyl)amine ligand ; Nonacoordinated strontium compound ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of 3,5-di-tert-butylcatechol and aqueous ammonia with boron, aluminum, gallium, or strontium chloride, or with calcium or barium acetate produce, under oxidizing conditions, neutral complexes of stoichiometric formulae ML (M = BCl), ML2, [M = Al (2), Ga (3), Ca (4), and Ba (5)], and ML3H [M = Sr (6)] [L = different oxidation states of bis(3,5-di-tert-butyl-1-hydroxy-2-phenyl)amine]. The structures of 1 and 4-6 were established by 1H- and 13C-NMR spectroscopy and of 2, 3, and 6 by X-ray diffraction. The coordination compound ClBL (1) was obtained by transmetallation of ZnL2 with BCl3. It is a tetracyclic compound with tetracoordinated boron and nitrogen atoms, the ligand being in the reduced form, bis(hydroxyphenyl)amine. The paramagnetic complexes 2 and 3 crystallized in the triclinic system and are hexacoordinated with two orthogonal planar ligands bonded to the metal atoms. The ligands appear in two different oxidation states: one as the monoanion and another as a radical dianion. Based on their X-ray diffraction molecular structures, it is deduced that both ligands have similar structures, confirming electronic delocalization and fast interconversion of their oxidation states. Ca and Ba complexes are diamagnetic and hexacoordinated, both ligands being monoanions The strontium complex crystallized in the monoclinic system, the metal atom is nonacoordinated, having two ligands as monoanions, and a third one is a neutral protonated diquinone. Its structure is a distorted helix with three paddles in a C3 geometry and its unexpected diamagnetic behaviour is due to the presence of a reduced protonated ligand.
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 217-224 
    ISSN: 1434-1948
    Keywords: Reaction mechanisms ; Cyclopalladation ; Acetic acid ; Pd-C bond stability ; Polynuclear species ; Palladium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The processes operating during the synthetic cyclopalladation reactions of imines in acetic acid have been studied from a kinetico-mechanistic point of view. These reactions include a fast initial coordination to the palladium through the N-donor atom of the imine, followed by the proper C-H bond activation to produce the acetato bridged dimeric species. At this point, the lability of the bridging acetato groups, the hydrolysis of the C-Pd bonds, and/or the hydrolysis of C=N exo bonds contribute to the generation of dark red polynuclear compounds. The processes occurring after the C-H activation have been followed kinetically, both from palladium acetate plus imine, and the synthetically pure isolated acetato dimers as starting materials. The kinetic and activation parameters have been found identical within experimental error whatever the starting material was (k323 = 1.5 × 10-4 s-1; ΔH# = 51 kJ mol-1; ΔS# = -163 JK-1 mol-1 ΔV# = +19 cm3 mol-1 for the 4-ClC6H4-CH=N-CH2-C6H5 imine derivative 1a). Acidolysis of C-Pd bonds has been found to occur in these polynuclear species. When alternative monomeric Cbenzylic-Pd bond-containing complexes are possible follow ups of the reactions produce them as final dead-end complexes (k323 = 2.2 × 10-5 s-1; ΔH# = 61 kJ mol-1; ΔS# = JK-1 mol-1 ΔV# ≈ 0 cm3 cm-1 for the [2,4,6-(CH3)3]C6H2-CH=N-CH2-[2-(CH3]C6[H4] imine derivative 3d). The same study has been carried out with primary amines in order to check the validity of the data if C=N bond hydrolysis is taking place in the imine derivatives with exo C=N bonds. For complexes with similar type of metallacycles, the results agree reasonably well with the proposed mechanism [k323 = 1.2·10-4 s-1, ΔH# = 46 kJ·mol-1, ΔS# = -180 J·K-1mol-1, ΔV# = -16 cm3·mol-1 for the polynuclear formation of the C6H5-CH2-NH2 derivative 4e; k323 = 3.0·10-4 s-1, ΔH# = 55 kJ·mol-1, ΔS
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 19 (1996), S. 410-419 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: General simple criteria to predict and analyze the influence on trickle-bed reactors behavior of three phenomena, namely, plug flow deviations, external wetting efficiency and external mass transfer resistance, are developed. Criteria predictions are compared with results arising from a comprehensive mathematical model widely employed to describe trickle-bed reactors behavior and with other particular criteria reported in the literature. Present criteria applications to different sets of experimental data exemplify their practical utility for various actual situations and verify their validity. Besides, they constitute simple tools to diagnose detrimental on trickle-bed reactors operation.
    Additional Material: 4 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 16 (1993), S. 35-39 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Experimental data are reported for ion exchange equilibria of binary systems on Amberlite IR-120 resin, at different temperatures and total ionic concentrations in aqueous solutions. These systems exhibit non-ideal behaviour in both phases, and the equilibrium characterization has been based on the law of mass action, using Wilson and Meisssner, and Kusik equations to correlate the activity coefficients in the resin and aqueous solutions, respectively. Equilibrium constants, standard thermodynamic properties (Gibbs free enthalpy changes, enthalpy and entropy) and Wilson binary parameters were obtained as functions of temperature.
    Additional Material: 4 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 210-215 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The kinetics of the pseudohomogeneous liquid phase synthesis of a high molecular weight ester in a stirred tank reactor using cobalt chloride as catalyst has been studied at various temperatures, catalyst concentrations, and acid/alcohol molar ratios. A kinetic model has been determined that predicts the experimental results quite well.
    Additional Material: 7 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 3 (1997), S. 1017-1024 
    ISSN: 0947-6539
    Keywords: autocatalysis ; coiled coil ; kinetics ; peptides ; self-replication ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A 32-residue α-helical peptide with a sequence similiar to that of the GCN4 leucine zipper region is shown to catalyze its own formation by accelerating the amide bond formation of a 17-residue peptide, preactivated as a thiobenzyl ester, and a 15-residue peptide with a N-terminal cysteine. The self-replication process displays parabolic growth characteristics as revealed by a detailed kinetic analysis. Control reactions with single-mutant peptides strongly support a mechanism in which a ternary and/or quaternary complex of the product with both peptide fragments act(s) as the catalytically active intermediate(s). Furthermore, these experiments reveal a remarkable sequence selectivity, as evidenced by the loss of autocatalytic activity as a result of a single replacement of leucine or valine residues with an alanine at the recognition interface.
    Additional Material: 11 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991), S. 105-108 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A turntable dynamometer has been constructed for the accurate measurement of power input and mixing applications in bench stirred tank reactors. The main feature of this device is a pneumatic bearing with complementary conical parts. The conical pneumatic bearing permitted to apply eccentric loads without affecting its stability. The static friction torque in the pneumatic bearing was very small, 4 × 10-4 Nm, and can be neglected in the experimental ranges of measured torques, i.e. from 5 × 10-3 to 2.21 Nm. In accordance with the instrumentation used, the deviations obtained with the apparatus are less than 10% at low torque readings. At moderate torques, deviations lower than 1% are routinely obtained. Several power input measurements show that the obtained data scatter is lower than 2.5%. The power input response in the turbulent regime is in agreement with dimensional analysis: the power input depends on the cube of the impeller speed. In addition, data obtained with a turbine impeller under ungassed conditions agree with the predictions of a published correlation, which takes into account several geometrical parameters.
    Additional Material: 4 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 19 (1996), S. 315-323 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Intermig impellers have been postulated as very efficient for mixing highly viscous non-Newtonian fluids (such as xanthan and mycelial broths). However, no formal characterisation has been published and no fair comparisons have been made, based on accurate power drawn measurements and using equal number of impeller stages and equal diameter, if compared (for example) with the performance of Rushton turbines. Characterisation of the shape, size, and evolution of the well-mixed zones or “caverns” were correlated with power drawn, for single and dual Rushton turbines and for one- as well as two-stage Intermig unslotted impellers. Cavern evolution studies were carried out in a mixing tank (diameter=0.205 m, H/T=1.6) equipped with an accurate air bearing dynamometer. Carbopol 940 (0.25 wt.-%) was used as a model, transparent fluid. Impeller to tank diameter ratio was 0.53 for both impellers. Caverns were visualised by injecting methylene blue in the well-mixed zones. A single Rushton turbine developed larger caverns if compared with one-stage Intermig of the same diameter under power drawn below 1.5 kW m-3. At higher power drawn, both impellers behaved very similarly, reaching a limit in cavern volume of about 40% of the total liquid volume, even at very high (20 kW m03) power drawn. A similar trend characterised dual combinations: below 3 kW m-3, dual Rushtons gave larger cavern volume if compared with the performance of two-stage Intermigs. In either case, power drawn higher than 3 kW m03 was sufficient to mix more than 90% of the liquid volume. The presence or absence of the slot in the Intermig did not influence cavern development. Experiments with a smaller if compared with those obtained with the larger Intermig (D/T = 0.53).
    Additional Material: 11 Ill.
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  • 10
    ISSN: 1434-1948
    Keywords: Trinuclear triangulo palladium complex ; 2-Hydroxyacetophenone N4-ethylthiosemicarbazone ; Dimethylformamide aggregation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The X-ray crystal structure of a palladium(II) complex of 2-hydroxyacetophenone N4-ethylthiosemicarbazone (H2Ap4E) shows it to be a triangular,trinuclear complex with bridging thiosemicarbazonato sulfur atoms. This species can be formed from a monomer on dissolution in DMF or directly from Li2PdCl4 and the thiosemicarbazone in methanol-ammonia solution.
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