Experimental and theoretical study of the reaction of the ethynyl radical with nitrous oxide, C2H + N2O

We investigated the rate constants and reaction mechanism of the gas phase reaction between the ethynyl radical and nitrous oxide (C(2)H + N(2)O) using both experimental methods and electronic structure calculations. A pulsed-laser photolysis/chemiluminescence technique was used to determine the absolute rate coefficient over the temperature range 570 K to 836 K. In this experimental temperature range, the measured temperature dependence of the overall rate constants can be expressed as: k(T) (C(2)H + N(2)O) = 2.93 × 10(-11) exp((-4000 ± 1100) K/T) cm(3) s(-1) (95% statistical confidence). Portions of the C(2)H + N(2)O potential energy surface (PES), containing low-energy pathways, were constructed using the composite G3B3 method. A multi-step reaction route leading to the products HCCO + N(2) is clearly preferred. The high selectivity between product channels favouring N(2) formation occurs very early. The pathway corresponds to the addition of the terminal C atom of C(2)H to the terminal N atom of N(2)O. Refined calculations using the coupled-cluster theory whose electronic energies were extrapolated to the complete basis set limit CCSD(T)/CBS led to an energy barrier of 6.0 kcal mol(-1) for the entrance channel. The overall rate constant was also determined by application of transition-state theory and Rice-Ramsperger-Kassel-Marcus (RRKM) statistical analyses to the PES. The computed rate constants have similar temperature dependence to the experimental values, though were somewhat lower.     

Total synthesis of 7'-desmethylkealiiquinone

The total synthesis of an analogue of the marine alkaloid kealiiquinone has been completed through application of an intramolecular Diels-Alder reaction of an imidazole-containing enyne. Oxidative aromatization of the lactone adduct and N-methylation facilitates C2-oxidation via the imidazolium salt. Conversion of the lactone to the phthalaldehyde derivative and then to the dihydroxybenzoquinone was achieved via a reaction with glyoxal in the presence of KCN. Esterification of the vinylogous diacid and deprotection provided 7'-desmethylkealiiquinone.     

Chelation controlled reductive amination of cyclic ketones to trans-4-methoxycyclohexylamines: 9-BBN reduction mediated with FeCl3

A novel trans-diastereoselective reductive amination of 4-substituted cyclohexanones is described using 9-BBN as reducing agent in the presence of FeCl₃. The method permits efficient synthesis of structurally diverse 4-trans-alkoxycyclohexylamines.     

Formation of high density amorphous ice by decompression of ice VII and ice VIII at 135 K

Monte Carlo computer simulations of ice VII and ice VIII phases have been undertaken using the four-point transferable intermolecular potential model of water. By following thermodynamic paths similar to those used experimentally, ice is decompressed resulting in an amorphous phase. These phases are compared to the high density amorphous phase formed upon compression of ice Ih and are found to have very similar structures. By cooling liquid water along the water/Ih melting line a high density amorphous phase was also generated.     

Synthesis of proton‐conducting membranes by the utilization of preirradiation grafting and atom transfer radical polymerization techniques

The atom transfer radical polymerization (ATRP) of styrene onto poly(vinylidene fluoride)‐graft‐poly(vinylbenzyl chloride) (PVDF‐g‐PVBC) membranes was investigated. Novel membranes were designed for fuel‐cell applications. The benzyl chloride groups in the PVDF‐g‐PVBC membranes functioned as initiators, and a Cu‐based catalytic system with the general formula Cu(n)X_n/ligand [where X is Cl or Br and the ligand is 2,2′‐bipyridyl (bpy)] was employed for the ATRP. In addition, 10 vol % dimethylformamide was added for increased solubility of the catalyst complex in styrene. The system was homogeneous, except for the membrane, when the initiator/copper halide/ligand/monomer molar ratio was 1/1/3/500. As anticipated, the fastest polymerization rate of styrene was observed with the copper bromide/bpy‐based catalyst system. The reaction rate was strongly temperature‐dependent within the studied temperature interval of 100–130 °C. The degree of grafting increased linearly with time, thereby indicating first‐order kinetics, regardless of the polymerization temperature. Furthermore, 120 °C was the maximum polymerization temperature that could be used in practice because the membrane structure was destroyed at higher temperatures. The degree of styrene grafting reached 400% after 3 h at 120 °C. Such a high degree of grafting could not be reached with conventional uncontrolled radiation‐induced grafting methods because of termination reactions. On the basis of an Arrhenius plot, the activation energy for the homogeneous ATRP of styrene was 217 kJ/mol. The prepared membranes became proton‐conducting after sulfonation of the polystyrene grafts. The highest conductivity measured for the prepared membranes was 70 mS/cm, which is comparable to the values normally measured for commercial Nafion membranes. The scanning electron microscopy/energy‐dispersive X‐ray results showed that the membranes had to be grafted through the matrix with both PVBC and polystyrene to become proton‐conducting after sulfonation. In addition, PVDF‐g‐[PVBC‐g‐(styrene‐block‐tert‐butyl acrylate)] membranes were also synthesized by ATRP. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 591–600, 2002; DOI 10.1002/pola.10146     

2-(1-Aryliminoethylidene)quinolylnickel(II) dibromides: Synthesis, characterization and ethylene dimerization capability

A series of 2-(1-aryliminoethylidene)quinoline derivatives (L1-L9) and the nickel(II) dibromides (C1-C9) thereof, were synthesized and characterized. The molecular structures of C2 (R¹ = Et, R² = H, R = Me) and C9 (R¹ = ⁱPr, R² = H, R = ⁱPr) were confirmed as being distorted tetrahedral at nickel by single crystal X-ray diffraction. On treatment with diethylaluminium chloride (Et₂AlCl) or ethylaluminum sesquichloride (EASC), these nickel pre-catalysts exhibited high activity for selective ethylene dimerization (0.89-3.29 × 10⁶ g mol⁻¹(Ni) h⁻¹) at 20 °C under 10 atm of ethylene. The influence of the reaction parameters on the catalytic behaviour was investigated for these nickel systems, including variation of Al/Ni molar ratio and reaction temperature.     

Determination of the total carbon in soft drinks by tungsten coil electrothermal vaporization inductively coupled plasma spectrometry

A method is developed for the direct determination of carbon in soft drinks by electrothermal vaporization inductively coupled plasma atomic emission spectrometry. A tungsten coil is used as the electrothermal vaporizer, and is extracted from a commercially produced 150 W, 15 V microscope bulb. The standard additions method is employed to correct any matrix effects from the samples. Carbon emission is monitored at 193.091 nm. Carbon content determined for the samples was in the range of 13 to 60 g in one 8 fl oz serving, and these values agreed with the label values in the range 93 to 137% (except for one sample, Orange Fanta, which provided a 200% recovery. This was likely due to non-carbohydrate carbon-containing species in that sample). The precision of the technique was always better than 20% relative standard deviation (n = 10). The detection limits for carbon range from 0.4 to 3 mg L^{− 1}, and absolute detection limits range from 12 ng to 90 ng for a 30 μL aliquot of sample on the coil. This method could be an alternative approach for determining the carbon content of nonvolatile compounds, and complement HPLC–ICP-AES determination of those same species.     

Ultrasonic speeds and isentropic compressibilities of 2-methylpentan-1-ol with hexane isomers at 298.15 K

Ultrasonic speeds were determined for binary mixtures of 2-methylpentan-1-ol with n-hexane and each of its four isomers. Measurements were made over the whole mole-fraction range with particular attention given to the region of high dilution with respect to the alcohol. The results were combined with excess molar volumes reported previously to obtain values of the excess molar quantity $\text{K}{}_{\mathrm{<mtext>S,</mtext><mtext>m</mtext>}}{}^{\mathrm{<mtext>E</mtext>}}\text{= ?(}\text{?V}{}_{\mathrm{m}}{}^{\mathrm{E}}\text{?p}\text{)}{}_{\mathrm{s}}$ and the corresponding partial molar derivatives.     

低温加氢催化剂的设计: 理论与实践

简要总结了我们在C=C及C=O双键低温加氢双金属催化剂方面的最新研究成果. 首先, 我们以环己烯加氢为探针反应, 证明了平行使用多种研究手段的重要性, 包括单晶表面的基础研究与DFT计算, 多晶表面的合成与表征, 负载型催化剂的制备与性能测试等. 其次, 总结了双金属催化剂在其他加氢反应, 如丙烯醛C=O双键的选择性加氢, 苯的低温加氢, 以及乙炔的选择性加氢等反应中的应用. 最后, 讨论了利用金属碳化物代替贵金属Pt以减少双金属催化剂中Pt用量的可能性.