介绍了Kirk—Othmer Encyclopedia of Chemical Technology（化工技术百科全书）（第五版）电子图书网络版数据库，并对该数据库使用方法和检索途径作出了说明，且结合实例简单地介绍了该数据库的检索方法。

Kirk-Othmer Encyclopedia of Chemical Technology数据库介绍及实例

This Account reports the synthesis and characterization of dendrimer-encapsulated metal nanoparticles and their applications to catalysis. These materials are prepared by sequestering metal ions within dendrimers followed by chemical reduction to yield the corresponding zerovalent metal nanoparticle. The size of such particles depends on the number of metal ions initially loaded into the dendrimer. Intradendrimer hydrogenation and carbon−carbon coupling reactions in water, organic solvents, biphasic fluorous/organic solvents, and supercritical CO2 are also described.

http://rcrooks.cm.utexas.edu/research/resources/Publications/rmc113.pdf

Dendrimer-Encapsulated Metal Nanoparticles: Synthesis, Characterization, and Applications to Catalysis

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Organic Chemistry By Dr. I. L. Finar. Vol. 2: Stereochemistry and the Chemistry of Natural Products. Pp. xi + 733. (London and New York: Longmans, Green and Co., Ltd., 1956.) 40s. net.

Advanced Organic Chemistry

Metal-mediated reductive hydrodehalogenation of organic halides.

Solid acids prepared by adding sulfuric acid on silica gel have been used as catalysts in the nitration of nitrobenzenes and their properties have been tested by kinetic studies at 25°C. Nitration rates in concentrated aqueous solutions of sulfuric acid were also analysed and the catalytic efficiencies of sulfuric acid in liquid and solid phase were compared by using kinetic data of analogous compounds. The results show that the solid acid samples exhibit nitrating properties very similar to those observed in concentrated aqueous solutions of sulfuric acid (range of 90 wt%). The relationship between nitration rates and effective concentration of electrophilic species [NO
 2
 +
 ], determined by studying the protonation–dehydration equilibrium of nitric acid in strong acids (HNO3 + H+ ⇌ H2O + NO
 2
 +
 ), was tested to better understand the acidity properties of medium.

/pdf/on-the-acidity-of-liquid-and-solid-acid-catalysts-part-2-a-4twfimdvey.pdf

On the acidity of liquid and solid acid catalysts. Part 2. A thermodynamic and kinetic study for acid-catalysed nitrations

Reaction rates and equilibrium constants of indole dimerization and trimerization in aqueous sulfuric acid at 298 K are reported. The equilibrium of oligomerization is attained in about 4–5 h, and formation of oligomers with more than three monomeric unit is not observed. The equilibrium of formation of the indole dimer is influenced by the protonation equilibrium of indole, which means the pKIH values of indole strongly influences equilibria and kinetics of the whole process. In the evaluation of the kinetic constants, the pKIH values of indole have been taken into account; in this way, the kinetic constant of formation of the dimer (kD) results almost four order of magnitude larger than that of the trimer (kT), suggesting a higher electrophilicity of the 3H-indolium cations with respect to the protonated dimer (which is an aliphatic ammonium salt). Further indole addition to the trimer, which is a protonated 2-alkyl-aniline, does not occur, since the anilinium ion is ineffective as an electrophile. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 107–112, 2009

Thermodynamics and kinetics of indole oligomerization: Preliminary results in aqueous sulfuric acid

The kinetics of phenol cyclohexylation catalyzed by sulfonic resins is studied taking into account equilibria and side reactions observed in the reaction media. The influence of different sulfonic resins has been tested and only small variation of the catalyst activity, referred to the acid amount, has been observed. Besides, the selectivity is unaffected by varying the type of the catalyst. The effect of reagent concentration on the reaction rate has been also studied, together with the reactivity of the cyclohexyl phenyl ether as intermediate. The etherification equilibrium of cyclohexyl phenyl ether has been analyzed in the presence of methanesulfonic acid, and the adsorption equilibria on a sulfonic resin of reagents and intermediates are measured, too. Starting from the evidences obtained from these studies an Eley–Rideal type kinetic model has been proposed and the fitting of the experimental data allows obtaining the kinetic constant of each stage. Good reliability of the model with the experimental data has been observed, also at high conversion, and the values of the fitting parameters are substantially constant by varying the operative variable, which is a further proof of the goodness of the model.

/pdf/kinetics-and-mechanism-of-acid-catalyzed-alkylation-of-248inj4yol.pdf

Kinetics and mechanism of acid catalyzed alkylation of phenol with cyclohexene in the presence of styrene divinylbenzene sulfonic resins

The title complex is highly active and selective for the alternating copolymerisation of carbon monoxide and ethene in CH 3 COOH–H 2 O as a solvent. Under typical reaction conditions, 90 °C, 4.5 MPa, CO/ethene = 1/1, the productivity passes through a maximum of 15,500 gPK (gPd h) −1 when the concentration of the acid is 40% (mol mol −1 ), whereas the limiting viscosity number (LVN) increases upon increasing the acid concentration. Under the above conditions, but in the presence of sodium acetate, a polyketone (PK) of higher molecular weight is obtained, though at the expense of the productivity. Under higher pressure of ethene both productivity and LVN increase; under higher pressure of CO the productivity slightly decreases, whereas the LVN increases. These results are discussed taking into account the factors relevant to the chain growing and the termination processes.

Selective alternating copolymerisation of carbon monoxide and ethene catalysed by [PdCl2(dppf)] in acetic acid-water as a solvent [dppf= 1, 1' -bis (diphenylphosphino )ferrocene]

Abstract The use of CO2 as a feedstock for chemical synthesis is considered as a viable alternative option to some traditional processes. One of the most interesting challenge for the industry is represented by the CO2 coupling with olefins to produce acrylate. Only recently, with the choice of suitable ligands and the use of a sacrificial base, a selective catalytic reaction was established by using Ni(0)-based complexes. The one-pot reaction, which leads to the highest TON (107 mol/mol Ni, in 20 h) reported so far, was successfully developed starting from Ni(0)-based precursors in the presence of disphosphine ligands, a large excess of base and of finely powdered zinc. In the present paper, we carried out the catalytic synthesis of sodium acrylate from CO2 and ethene, in one-pot, by using Ni(II)-chloride and Pd(II)-chloride phosphine-complexes as precatalyst. The reaction occurs under basic conditions and without adding any external reductants. The Ni(II) complexes lead to higher TON than the respective Pd(II) precursors and the best results are obtained by using diphosphines having high bite angles. Such catalysis is favored by aprotic and polar solvents in which a TON of 290 mol/mol Ni is reached by using the [NiCl2(dppp)] precursor in DMSO. Furthermore the TON could be increased by increasing the temperature, the base concentration and by using diphosphine ligands having high bite angle.

The coupling of carbon dioxide with ethene to produce acrylic acid sodium salt in one pot by using Ni(II) and Pd(II)-phosphine complexes as precatalysts

Lucio Ronchin

Papers

On the acidity of liquid and solid acid catalysts. Part 2. A thermodynamic and kinetic study for acid-catalysed nitrations

Thermodynamics and kinetics of indole oligomerization: Preliminary results in aqueous sulfuric acid

Kinetics and mechanism of acid catalyzed alkylation of phenol with cyclohexene in the presence of styrene divinylbenzene sulfonic resins

Selective alternating copolymerisation of carbon monoxide and ethene catalysed by [PdCl2(dppf)] in acetic acid-water as a solvent [dppf= 1, 1' -bis (diphenylphosphino )ferrocene]

The coupling of carbon dioxide with ethene to produce acrylic acid sodium salt in one pot by using Ni(II) and Pd(II)-phosphine complexes as precatalysts