Competitive Intramolecular Aryl‐ and Alkyl‐C?H Bond Activation and Ligand Evaporation from Gaseous Bisimino Complexes [Pt(L)(CH3)((CH3)2S)]+ (L=C6H5NC(CH3)?C(CH3)NC6H5)

Mechanistic details for the formation of methane from the title compound as well as the combined elimination of (CH₃)₂S/CH₄ are derived from various mass‐spectrometric experiments including deuterium‐labeling studies and DFT calculations. For the first process, i.e., methane formation, we have identified three competing pathways in which the intact, Pt‐bonded methyl group combines with a H‐atom that originates from a phenyl substituent (ca. 7%), the dimethyl sulfide ligand (ca. 41%), and a methyl group of the diazabutadiene backbone (ca. 52%). In contrast, in the combined (CH₃)₂S/CH₄ elimination, the methane is specifically formed from the Pt‐bound CH₃ group and a H‐atom provided by one of the phenyl groups (‘cyclometalation’).     

Synthesis of N‐alkyl‐N′‐aryl or Alkenylpiperazines: A Copper‐Catalyzed C–N Cross‐Coupling in the Presence of Aryl and Alkenyl Triflates and DABCO

Unsymmetrical piperazines are key constituents of many pharmaceuticals. Given that the selective introduction of an aryl and alkyl motif onto the piperazine is not always straightforward, direct arylation and alkenylation of 1,4‐diaza‐bicyclo[2.2.2]octane would obviate the inefficiencies associated with the preparation of these target molecules. We have utilized alkyl halides, aryl or alkenyl triflates, and 1,4‐diaza‐bicyclo[2.2.2]octane for the synthesis of N‐alkyl‐N ′‐aryl or alkenylpiperazines. The optimum conditions are developed using CuCl, t‐BuOL i in NMP . Alkenyl triflates requires N ,N ′‐dimethylethylenediamine and higher temperature to afford the desired cross‐coupled product. Substrates bearing electron‐deficient and electron‐rich groups were successfully coupled under the optimum reaction conditions.     

Synthesis and crystal structure of CuZrTiO5—A new crystal structure type

A new compound, CuZrTiO₅, was synthesized as strongly pleochroic green crystals from the oxides between 995 and 1010 °C, 1 atm. Its crystal structure was determined by single crystal XRD, resulting in R (F²>2σ(F²))=0.032 and wR (all data)=0.079). CuZrTiO₅ is orthorhombic, space group P2₁2₁2₁, a=3.5871(3) Å, b=6.6968(4) Å, c=14.6679(9) Å, V=352.35(4) Å³, Z=4. The structure is topologically similar to In₂TiO₅ but differs in space group and cation coordination. CuZrTiO₅ has relatively regular TiO₆ polyhedra, but coordination is 7+1 for Zr, and 4+2 for Cu due to the Jahn-Teller effect. Ordering of the long Cu-O bonds causes reduction in symmetry relative to In₂TiO₅. Layers of Cu alternate with Ti+Zr on (001), giving rise to a distinct cleavage. Bond valence sums on Ti and Zr are far from ideal, which appears due to the limited ability of this structural topology to avoid close next-nearest neighbour distances.     

N—O键解离焓的密度泛函理论研究

在高精度计算方法G3和G3B3的基础上,比较了密度泛函理论(DFT)十几种方法对N—O键解离焓(BDE)相对于实验值的计算精度,发现用B3P86方法计算15种化合物N—O键的BDE,均方根误差最小,仅为6.36kJ·mol-1,计算值与实验值的线性相关系数为0.991.在此基础上,用该方法分别计算了非芳香化合物及芳香化合物的N—O键BDE.通过自然键轨道分析,发现部分N—O键的BDE与N—O键的键长、原子电荷密度及键级之间存在定量关系.此外,在B3P86方法的基础上预测了几种典型的杂环芳香化合物N—O键BDE值.     

High-resolution infrared spectrum of cyanogen

The high-resolution spectrum of cyanogen (¹⁴N¹²C¹²C¹⁴N) has been measured from 500 to 4900 cm⁻¹. For this isotopomer many combination levels with both degenerate fundamentals, ν₄ and ν₅, have been measured for the first time and the effects of vibrational l-type resonance are observed as well as rotational l-type resonance. The effects of the vibrational resonance coupling ν₂ and 2ν₄ have also been studied. The data have been combined with earlier measurements below 500 cm⁻¹ to give a comprehensive catalog of the vibrational energy levels and the rovibrational constants for the normal isotopomer of cyanogen. A comparison of the term value constants for the three major symmetric isotopomers is given and they are compared with a recent ab initio calculation. The present data were combined with earlier work on the two symmetric isotopomers, ¹³C₂¹⁴N₂ and ¹²C₂¹⁵N₂, to obtain the equilibrium bond lengths, r_CC = 138.109(60) pm and r_CN = 115.976(40) pm.     

Role of cleaning methods on bond quality of Ti coated glass/imidex system

Thin film materials are widely used in the fabrication of semiconductor microelectronic devices. In thin film deposition, cleanliness of substrate surface have become critically important as over 50% of yield losses in integrated circuit fabrication are caused by microcontamination [1]. There are many wafer cleaning techniques. The most successful approach for silicon wafer cleaning technique is RCA clean [2]. But for glass substrate it is still not known which procedure of cleaning is the best. This paper provides an understanding of the right way of glass wafer cleaning method, with a focus towards identifying good bond strength. Two wafer cleaning techniques have been used for cleaning glass substrates in the context of laser micro-joining of dissimilar substrates. First cleaning procedure involves two steps, first cleaning in acetone solution and then in DI water solution. After each step dried with N₂. Second cleaning procedure involves four steps, first cleaning with 1% Alconox solution, second in DI water, third in acetone solution and finally in a methanol solution and dried with N₂ after each step. Deposition of Ti thin film on top of these two types of substrate using DC magnetron sputtering method also showed better adhesion of Ti film on glass for the second type of cleaning method. Scanning electron microscopy (SEM) analyses of the lap shear tested failed surfaces for these two kinds of samples revealed strong bond for samples prepared by second cleaning method compared to first cleaning method. Characterization of these two sets of samples using X-ray photoelectron spectroscopy (XPS) has shown excellent contamination removal for the second cleaning method. This modification is believed to be due to reduction of carbon contamination.     

Effects of the bond dilution on the phase diagrams of a spin-1 transverse Ising model with crystal field interaction on a honeycomb lattice

A bond diluted spin-1 Ising model with crystal and transverse field interactions is examined for honeycomb lattice by introducing an effective field approximation that takes into account the correlations between different spins that emerge when expanding the identities. The effects of the crystal field as well as the transverse field and dilution on the phase diagrams and order parameter m_z are discussed in detail. A number of interesting and unusual phenomena such as reentrant phenomena and three successive phase transitions originating from the crystal field as well as the transverse field and bond dilution have been found.     

Comparison of theoretical methods for assessing the heat of formation of C1 and C2 chlorofluorocarbons and hydrochlorofluorocarbons

The heat of formation of a number of key C₁ and C₂ chlorofluorocarbons and hydrochlorofluorocarbons have been calculated by G3, G3MP2, G3MP2B3 and G3B3 methods. Based on the results of the atomization approach, it was found that the errors are approximately dependent upon the number of C-F or C-Cl bonds. Moreover, the bond additive correction (BAC) procedure and isodesmic reactions approach improved the accuracy and decreased these system errors significantly. The extended comparison between the BAC procedure and isodesmic reaction approaches had been made; the latter yielded the best results and showed broader applicability.     

一类可调转股价可转债的定价分析与计算

1 引言可转换债券以其独特的风险受益特性逐渐为投、融资者所接受并得到了广泛的欢迎．如今,无论在广度还是深度上,全球范围的可转债市场都已经发生了质的变化,并且日趋成熟和繁荣．中国的可转债市场在经历了十余年的沉寂之后,近两年也正进入一个高速发     

Thiophenol and thiophenol radical and their complexes with gold clusters Au5 and Au6

The longstanding controversy between experiment and theory regarding which conformer of thiophenol, planar or perpendicular, is the most stable and what is the magnitude of the corresponding rotational barrier of the S–H group is discussed. We propose a variety of rather modest high-level computational methods within the density theory, which corroborate the experimental data. These methods demonstrate that the planar structure of thiophenol is the most stable and the magnitude of the rotational barrier falls within the experimental range of 3.35±0.84 kJ mol⁻¹. However, the barrier is of the order of RT at room temperature, which might prevent to clearly identify the most stable conformer of thiophenol in experiments and leads to a large-amplitude motion of the thiolic hydrogen. On the other hand, such low value of the barrier may lead to some error in evaluating the thermodynamic properties of thiophenol within the rigid-rotor-harmonic oscillator model, in particular for the bond dissociation enthalpy. We also show the existence of a large entropy contribution to the Gibbs free energy difference between the planar and perpendicular conformers which is the order of the rotational barrier (≈4 kJ mol⁻¹). This might be of interest for experimental study. The most stable complexes of thiophenol with the gold clusters Au₅ and Au₆ are also investigated. It is shown that the sulfur atom prefers to anchor to two- and three-coordinated atoms of gold in these clusters to form a strongly directional gold–sulfur bond. The hydrogen abstraction from the S–H group of thiophenol bonded to the two-coordinated gold atom in Au₅ yields the bridging Au–S dibond and results in a spectacular reduction of the bond dissociation energy of thiophenol by nearly a factor of three.