Experimental and quantum chemical study of pyrrole self-association through N-H?π hydrogen bonding

An FT-IR study of pyrrole self-association in CCl₄ solutions was carried out. According to the IR measurements, pyrrole forms self-associated dimeric species via N-H?π hydrogen bonding. This was also confirmed by quantum chemical calculations for pyrrole monomer and dimer at B3LYP/6-31++G(d,p) level of theory. A T-shaped minimum was located on B3LYP/6-31++G(d,p) PES of pyrrole dimer characterized with a hydrogen bond of an N-H?π type, with centers-of-mass separation of monomeric units of 4.520 Å, H?π distance of 2.475 Å, the interplanar angle between the two monomeric units being 72.9°. The anharmonic vibrational frequency shift upon dimer formation calculated on the basis of 1D DFT vibrational potentials is in excellent agreement with the experimental data (84 vs. 87 cm⁻¹). Harmonic vibrational analysis predicts somewhat smaller shift (68 cm⁻¹). On the basis of NIR spectroscopic data, anharmonicity constants for the 2ν(N-H) and 2ν(N-H?π) vibrational transitions were calculated. The orientational dynamics of monomeric and self-associated pyrrole species was studied within the framework of the transition dipole moment time correlation function formalism. The period of essentially free rotation in the condensed phase reduces from 0.05 ps for the monomeric pyrrole to 0.02 ps for the proton-donor molecule within the dimer.     

金属氢研究新进展

简要介绍了金属氢的研究意义和应用前景 ,详细评述了有关的高压实验方法和最近的研究成果及进展 ,特别是固体氢的相图、结构和相变 .近十多年来 ,随着超高压技术的发展 ,已能在金刚石对顶砧 (DAC)上产生30 0GPa的静态压力 ,并可进行高压原位实验研究 .对固体氢进行了高压拉曼、同步辐射X射线、光反射和吸收、同步辐射红外光谱等一系列高压物性和相变研究 .从而确定了固体氢的三个相 ,并提出了可能的相结构 .     

Electrocatalytic Oxidation of H_2 O_ 2 at a Carbon Paste Electrode Modified with a Nickel (Ⅱ)-5,11,17,23-Tetra-Tert-Butyl-25,27-Bis(Diethylcarbamoylmethoxy)Calix[4] Arene Complex and Its Application

0　IntroductionThegreatimportanceofnickelelectrochemistryinalkalinemedium ,especiallyforpotentialapplication ,hasattractedmuchattetionofresearcherseithertostudythebehaviorofnickel basedelectrodeitselforitsactivitytowardsothermolecules.Manyreportsshowedthatthenickelbasedelectrodeshaveelectro catalyticactivityforreactionsofappliedinterest,suchaselectro chemicaldeterminationofantioxidantsinfood[1 ] ,detectionofni tricoxide (NO )insolution[2 ] ,electrocatalyticoxidationofmethanol[1 ] ,alcohol[3] ,…     

析氢反应动力学的交流阻抗法研究

利用交流阻抗法测定析氢电化学动力学参数，得到与极化曲线法一致的结果，为确定复杂析氢过程速率的决定步骤提供了判据。     

Kinetic features of ethylene polymerization over supported catalysts [2,6‐bis(imino)pyridyl iron dichloride/magnesium dichloride] with AlR3 as an activator

The effects of polymerization temperature, polymerization time, ethylene and hydrogen concentration, and effect of comonomers (hexene‐1, propylene) on the activity of supported catalyst of composition LFeCl₂/MgCl₂‐Al(i‐Bu)₃ (L = 2,6‐bis[1‐(2,6‐dimethylphenylimino)ethyl] pyridyl) and polymer characteristics (molecular weight (MW), molecular‐weight distribution (MWD), molecular structure) have been studied. Effective activation energy of ethylene polymerization over LFeCl₂/MgCl₂‐Al(i‐Bu)₃ has a value typical of supported Ziegler–Natta catalysts (11.9 kcal/mol). The polymerization reaction is of the first order with respect to monomer at the ethylene concentration >0.2 mol/L. Addition of small amounts of hydrogen (9–17%) significantly increases the activity; however, further increase in hydrogen concentration decreases the activity. The IRS and DSC analysis of PE indicates that catalyst LFeCl₂/MgCl₂‐Al(i‐Bu)₃ has a very low copolymerizing ability toward propylene and hexene‐1. MW and MWD of PE produced over these catalysts depend on the polymerization time, ethylene and hexene‐1 concentration. The activation effect of hydrogen and other kinetic features of ethylene polymerization over supported catalysts based on the Fe (II) complexes are discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5057–5066, 2007     

催化裂解法制备螺旋状碳纳米管的实验研究

在硅片上用直流溅射镀铁的方法制备催化剂 ,通过乙炔在 70 0°C下催化裂解制备碳纳米管 .对热解产物进行了扫描电镜观察和 X射线衍射测试 .本文通过对有氢气预处理和没有氢气预处理两种情况下催化裂解法制备的碳纳米管的形貌、管径大小等性质的研究 ,来初步揭示螺旋状碳纳米管的生长机理 .     

A supramolecular hydrogen‐bonded complex between 1,3,5‐tris(diisobutylhydroxysilyl)benzene and trans‐bis(4‐pyridyl)ethylene

The trisilanol 1,3,5‐(HOi‐Bu₂Si)₃C₆H₃ ( 7 ), prepared in three steps from 1,3,5‐tribromobenzene via the intermediates 1,3,5‐(Hi‐Bu₂Si)₃C₆H₃ ( 8 ) and 1,3,5‐(Cli‐Bu₂Si)₃C₆H₃ ( 9 ) forms an equimolar complex with trans‐bis(4‐pyridyl)ethylene (bpe), 7 ·bpe, whose structure was investigated by X‐ray crystallography. The hydrogen‐bonded network features a number of SiO? H(H)Si and SiO? H hydrogen bridges. Evidence was found for cooperative strengthening within the sequential hydrogen bonds. Copyright © 2007 John Wiley & Sons, Ltd.     

Catalysis by Ir(III), Rh(III) and Pd(II) metal ions in the oxidation of organic compounds with H2O2

Catalytic activities of three transition metals, as iridium (III) chloride, rhodium (III) chloride and palladium (II) chloride, were compared in the oxidation of six aromatic aldehydes (benzaldehyde, p‐chloro benzaldehyde, p‐nitro benzaldehyde, m‐nitro benzaldehyde, p‐methoxy benzaldehyde and cinnamaldehyde), two hydrocarbons (viz. (anthracene and phenanthrene)) and one aromatic and one cyclic alcohol (cyclohexanol and benzyl alcohol) by 50% H₂O₂. The presence of traces (substrate: catalyst ratio equal to 1:62500 to 1:1961) of the chlorides of iridium(III), rhodium(III) and palladium(II) catalyze these oxidations, resulting in good to excellent yields. It was observed that in most of the cases palladium(II) chloride is the most efficient catalyst. Conditions for the highest and most economical yields were obtained. Deviation from the optimum conditions decreases the yields. Oxidation in aromatic aldehydes is selective at the aldehydeic group only and other groups remain unaffected. This new, simple and economical method, which is environmentally safe, also requires less time. Reactive species of catalysts, existing in the reaction mixture are also discussed. Copyright © 2007 John Wiley & Sons, Ltd.     

Effect of hydrogen on interatomic bonds in austenitic steels

Mössbauer spectroscopy was used to investigate the influence of dissolved hydrogen on the interatomic bonds in austenitic steels. It was carried out to prove the decohesion mechanism of hydrogen embrittlement (HE). It is shown that hydrogen increases Debye temperature, i.e., the interatomic bonds in hydrogenated austenitic steel becomes stronger.