NH2(～X2B1)与CH4反应机理的理论研究

在密度泛函理论B3LYP／6－311G^*水平下，研究了NH2与CH4的反应机理。通过振动频率和内禀反应坐标（IRC）分析，对反应过渡态进行了确认。在QCISD（T）／6－311G^*水平下进行了单点能计算，并进行了零点能校正，结果表明，反应NH2＋CH4→N3＋CH3是主要的反应通道。     

N,N'-二(二乙氧基硫代磷酰基)-1,4-苯二胺的合成、晶体结构及热性能研究

通过二乙氧基硫代磷酰氯与对苯二胺反应生成了标题化合物N,N'-二(二乙氧基硫代磷酰基)-1,4-苯二胺，并应用元素分析, FTIR及¹H NMR对标题化合物进行了表征. 利用X射线单晶衍射测定了其晶体结构, 同时应用TG分析法对其热性能进行了分析. 标题化合物的相对分子质量M_r＝412.42, 为正交晶系, Pbca空间群, 晶胞参数为a＝0.86936(16) nm, b＝1.2787(2) nm, c＝1.8897(3) nm, β＝90°, V＝2.1006(7) nm³, Z＝8, D_c＝1.304 g/cm³, μ(Mo Kα)＝0.425 mm^－1, F(000)＝872, S＝1.052. 最终偏离因子R＝0.0628, wR＝0.1860, 可观测衍射点1852个[I＞2σ(I)]. 该晶体通过对苯二胺连接并以中心对称分布, 并形成层状结构, 且存在弱的分子内氢键N—H…S. TG分析表明该化合物有很好的热稳定性及成炭性, 通过其阻燃聚丙烯腈表明, 该物质是一种高效能的膨胀型阻燃剂.     

化学衍生-高效液相色谱法测定硫氰酸根阴离子

以α-溴-2,3,4,5,6-五氟甲苯作柱前衍生试剂,经优化衍生和色谱条件,实现了用高效液相色谱法测定硫氰酸根离子。在ODS柱上,用甲醇-水(80:20)作流动相,于254nm检测,得到线性关系良好的工作曲线,最小检测限为4.7ng。分析了吸烟者唾液样品,回收率为93.7％～101.4％。     

VOCl_3/Et_3Al_2Cl_3/CCl_4溶剂体系催化乙烯丙烯共聚

本文以VOCl_3/Et_3Al_2Cl_3为催化剂,在CCl_4溶剂中进行乙烯共聚反应。在聚合过程中,发生一异常的颜色突变现象。颜色突变后,体系催化聚合生成分子量很低的产物。从聚合物的结构表征及机理探讨表明:颜色突变后,体系产生了新的活性中心,催化机理发生了转变——由配位机理转变为阳离子机理。     

Synthetic receptors based on calix[4]arene functionalized at the lower rim in molecular recognition of dicarboxylic, α-hydroxycarboxylic,and α-amino acids

New calix[4]arenes, di- and tetrasubstituted at the lower rim, with different functional groups were synthesized. They were studied as carriers of a series of dicarboxylic and -hydroxycarboxylic acids through a liquid impregnated membrane. The calix[4]arenes under study are capable of molecular recognition of oxalic acid in the series of structurally similar dicarboxylic and -hydroxycarboxylic acids. The regularities found make it possible to change purposefully the receptor ability of 1,3-disubstituted calix[4]arenes by variation of the nature of substituents.     

OXIDATIVE COUPLING OF METHANE OVER Mn_2O_3-Na_2WO_4/SiO_2 CATALYST Ⅰ.CHARACTERIZATION OF ACTIVE SITES ON THE CATALYST

EPR and Raman spectroscopy have been used to characterize the catalyst. F-centers with EPR parameter of g=2. 0046 form when gas phase oxygen is admitted onto the catalyst reduced with methane at 800℃- Molecular oxygen plays an induced role in the electron transfer from W4 to the oxygen ion vacancy which is produced by methane reduction. Raman spectra give the further evidence for the production of lattice oxygen from molecular oxygen.     

The importance of nonconventional structures in the binding of Ni<Superscript>+</Superscript> to ethynylsilanes and ethynylgermanes

The influence of the nature of the heteroatom on the Ni⁺ gas-phase binding energies of HCC–XH₃ (X is C, Si, or Ge) compounds has been investigated through the use of high-level density functional theory methods. The structures of the corresponding Ni⁺ complexes were optimized at the B3LYP/6-311G(d,p) level of theory. Final energies were obtained in single-point B3LYP/6-311+G(2df,2p) calculations. Nonconventional complexes, in which the metal cation interacts simultaneously with the CC system and with one of the X–H bonds of the substituent XH₃ group, play a significant role in the binding of Ni⁺ to HCC–XH₃ (X is Si or Ge) derivatives. Conversely, such nonconventional complexes are not local minima of the propyne–Ni⁺ potential-energy surface. This establishes a clear distinction between unsaturated carbon derivatives and the Si- and Ge-containing analogues as far as bonding to transition-metal monocations is concerned. Actually, the attachment of Ni⁺ to HCC–XH₃ (X is Si or Ge) compounds in the gas phase yields a mixture of conventional and nonconventional complexes. These agostic-type interactions can be viewed as a dative bond from the X–H bonding orbital toward the empty s orbital of the metal, and a back-donation from the valence electron pairs of the metal into the X–H antibonding orbital of the neutral species.Proceedings of the 11th International Congress of Quantum Chemistry satellite meeting in honor of Jean-Louis Rivail     

The Kissinger law and isokinetic effect: Part II. Experimental analysis

On the basis of copper sulphate pentahydrate thermal dissociation, for analyzed reactions I to IV, 6 thermokinetic equations was discussed. Arrhenius law parameters were determined and the isokinetic effect (IE) and Kissinger law appearing was analyzed. It was found that only dependence resulting from isokinetic effect, in the form k _m=q/T _m, relates to the suitable thermokinetic Eq. (2) and Kissinger law in modified form (14). The confirmation was made that the possibility of determining the averaged activation energy from thermokinetic equations using suitable correction coefficients exists.This revised version was published online in November 2005 with corrections to the Cover Date.     

A Convenient Method for the Preparation of Linear Furoquinolin-2-ones

Fries rearrangement of 7-acetoxy-4-methylquinolin-2-one and subsequent condensation of the 6-acetyl-7-hydroxy-4-methylquinolin-2-one obtained with -chloro ketones gives a series of furo[3,2-g]quinolin-7-ones.