Copper-Catalyzed Trifunctionalization of Alkynes: Rapid Formation of Oxindoles Bearing Geminal Diboronates

A copper-catalyzed trifunctionalization of alkynes that provides rapid access to oxindoles bearing a geminal diboronate side chain, highlighted by the simultaneous formation of one C−C bond and two C−B bonds, is reported. This new reaction features simple reaction conditions (ligand-free catalysis), a general substrate scope, and excellent chemoselectivity. Mechanistic study revealed a reaction sequence constituted by, in the order, borylation, intramolecular cross-coupling, hydroboration, which has been rarely documented.     

Chemical Composition and Antibacterial and Cytotoxic Activities of the Essential Oil of Plumbago zeylanica

Chemistry of Natural Compounds -     

Starlike nanostructures of polyoxometalates K3[PMo12O40].nH2O synthesized and assembled by an inverse microemulsion method

In a nonionic inverse microemulsion system, surfactant (C12-18EO9)/cyclohexane/water, heteropolyanions [PMo12O40]3- react with K+ to form K3[PMo12O40].nH2O nanorods and assemble as three-dimensional starlike nanostructures.     

用第一性原理方法获取周期体系中原子的部分电荷

利用量子化学软件包Crystal计算了立方周期性边界条件下液态水体系的静电势(ESP)和静电场(EF).在此基础上,提出了一种由第一性原理方法获取周期体系中原子的部分电荷的快捷方法.该方法把由周期性边界条件引入的平均静电势准mean作为一个拟合参数,通过对第一性原理静电势与Ewald加和法静电势的最小二乘法拟合而实现.值得说明的是,比较静电势与静电场拟合方法,前者的相对拟合误差仅为2%-3%,比后者小一个数量级.考察了四种电荷限制条件下,静电势、静电场拟合的水分子原子部分电荷及偶极矩的分布情况.     

Synthesis,crystal structure,spectroscopic properties and DFT calculations of a new Schiff base-type Zinc(II) complex

Research on Chemical Intermediates - A new mononuclear Zn(II) complex, [Zn(L 2 )2]·CH3OH (HL 2  = 1-(2-{[(E)-3,5-dichloro-2-hydroxybenzylidene]amino}phenyl)ethanone oxime),...     

Phase transfer catalyst supported, room-temperature biphasic synthesis: a facile approach to the synthesis of coordination polymers

A facile approach, named phase transfer catalyst supported, room temperature biphasic synthesis, has been developed to synthesize a new type of coordination polymers. Compared to the traditional biphasic solvothermal synthesis that was run at high temperature (100-200 °C), the new approach introduced here can be operated under a mild condition (room temperature) with the support of phase transfer catalyst. With the application of this new approach, two copper coordination complexes with 1D metal-organic nanotube and 1D coordination polymer containing large water clusters have been successfully synthesized and characterized. Furthermore, the synthetic approach presented here can be extended to synthesize other coordination polymers, including porous lanthanide-organic frameworks.     

A Polymeric Iodiplumbate(Ⅱ) Templated by Conjugated Quaternary Ammonium: Synthesis, Band Structure and Optical Properties

A new lead(Ⅱ) iodide coordination polymer [(npq)(PbI3)]n 1 (npq = N-propyl- quinolinium) has been synthesized in the presence of npq as structure-directing reagent (SDA). Compound 1 crystallizes in the orthorhombic system, space group Pbca, with a = 19.158(4), b = 7.9909(16), c = 22.929(5) (A), V = 3510.2(12) (A)3, Z = 8, Dc = 2.877 g/cm3, F(000) = 2672, C12H14I3NPb, Mr = 760.14, μ(MoKα) = 14.872 mm-1, the final R = 0.0431 and wR = 0.1021 for 3678 observed reflections with I＞2σ(I). Structure determination indicates that the [PbI3]-n infinite chains in each unit cell shape the sketch of 1, which could be described as the result of face-sharing distorted PbI6 octahedra running along the b axis. Electrostatic interaction between conjugated organic counter-cations and inorganic moieties presents and contributes to the crystal packing. 1 was further characterized with IR and elemental analysis. Based on the crystal structure data, quantum chemical calculation with DFT method was used to reveal the electronic structure and optical property of 1.     

Metal-free visible-light-mediated aerobic oxidation of silanes to silanols

Oxidation of silanes into silanols using water/air has attracted considerable attention. The known methods with no exception required a metal catalyst. Herein we report the first metal-free method: 2 mol% Rose Bengal as the catalyst, air(O2) as the oxidant, water as the additive and under visible light irradiation. While this method produces various silanols in a simple, costeffective, efficient(92%–99% yields) and scalable fashion, its reaction mechanism is very different than the reported ones associated with metal catalysis.     

Solid state electrochemical study of the phase diagram and thermodynamics of the ternary system CuGeO

Coulometric titrations using solid zirconia ionic conductors have been employed to determine the phase diagram of the ternary system CuGeO in the temperature range from 750 to 950°C. CuGeO₃ was found to be the only existing ternary compound in the system. It is in equilibrium with Cu₂O, CuO, GeO₂, and oxygen of atmospheric pressure. Cu and Cu₂O may coexist with GeO₂. The standard Gibbs energy of formation of CuGeO₃ was found to be ΔG°_f (CuGeO₃) = ?424.5 kJ/mole at 900°C. The standard enthalpy and entropy of formation are ΔH⁰_f = ?756.8 kJ/mole and ΔS°_f = ?283 J/mole·K, respectively.     

分子动力学模拟纳米尺寸限制体系下氩溶液中I2的振动能量弛豫

利用平衡态分子动力学方法(EMD)模拟了纳米尺寸限制球壳内I2在Ar溶液中的振动能量转移. 计算并讨论了I2振动能量弛豫时间T1随球壳半径、溶剂密度的变化规律. 通过分子间相互作用分析, 在原子、分子水平上, 揭示了随着球壳半径的减小, T1呈逐渐增大趋势的原因. 结果表明, 球壳的几何限制效应和表面作用对受限溶液密度分布的影响较大, 从而导致溶质振动弛豫的显著变化. 此外, 非限制体系模拟显示, 非平衡态分子动力学(NEMD)方法可以得到与平衡态分子动力学方法较一致的振动能量弛豫时间T1.