Novel Z-selective head-to-head dimerization of terminal alkynes catalyzed by lanthanide half-metallocene complexes

Various terminal alkynes have been cleanly dimerized into the corresponding head-to-head (Z)-enynes by use of the half-metallocene lutetium alkyl complexes Me2Si(C5Me4)(NAr)Lu(CH2SiMe3)(THF) (Ar = Ph, C6H3Me2-2,6, C6H2Me3-2,4,6) as catalysts. Aromatic C-Cl, C-Br, and C-I bonds, which are known to be extremely susceptible to reductive cleavage by transition metals, survived in the present reactions. The corresponding dimeric alkynide species [Me2Si(C5Me4)(NAr)Lu(mu-CCR)]2 are thought to be the true catalysts, some of which have been isolated and structurally characterized. These alkynide species were thermally stable and soluble at the reaction temperatures (80-110 degrees C), but they precipitated upon cooling to room temperature after completion of the reaction. Therefore, this catalyst system works homogeneously but can be separated and reused, thus constituting the first example of a recyclable catalyst system for the dimerization of terminal alkynes and also the first example of (Z)-selective head-to-head dimerization of aromatic terminal alkynes.     

同时测定食用植物油中抗氧剂叔丁基对羟基茴香醚和2，6－二叔丁基对甲酚的方法

报道了用高效液用色谱法同时测定食用植物油中的抗氧剂叔丁基对羟基茴香醚（ＢＨＡ）和２，６－二叔丁基对甲酚（ＢＨＴ）的实验方法。采用ＺｏｒｂａｘＯＤＳＣ_（１８）色谱住，甲醇：水（９０：１０，Ｖ／Ｖ）作流动相，检测波长为２４５ｎｍ，流速为１ｍＬ／ｍｉｎ。检测下限分别为１５ｎｇ（ＢＨＡ），９０ｎｇ（ＢＨＴ），回收率分别是９６．８％±９．８％（ＢＨＡ），９９．０％±３．２％（ＢＨＴ）。方法快速、准确，灵敏度高。     

The global topological meaning of cocycles in a Gauge group

This Letter shows explicitly that the descent sequence of cocycles in a gauge group realizes the ech-de Rham double complex. Meanwhile the ech complex corresponds to finite gauge transformations. This Letter also shows how the indices of each order of cocycles characterizes the obstructions on overlapping spheres in different dimensions and how these indices are equal to a common one.     

硫脲化合物的合成及其生物活性

硫脲化合物的合成及其生物活性董燕红，司宗兴（北京农业大学应用化学系北京１０００９４）关键词噻二陛－甲酰基，硫脲，胺类，合成，生物活性酰基硫脲在抗真菌、抗结核、抗病毒、除草以及调节植物生长方面具有广泛应用［１，２］。１，２，３－噻二唑杂环作为有效前体正...     

Self-assembly of a series of novel metal-organic compounds containing ferrocenecarboxylate components

Using FcCOONa (Fc = (eta(5)-C(5)H(5))Fe(eta(5)-C(5)H(4))) as starting material, we obtained an unprecedented metal-organic coordination polymer containing ferrocenecarboxylate components [[Pb(2)(FcCOO)(eta(2)-FcCOO)(mu(2)-eta(2)-FcCOO)(mu(3)-eta(2)-FcCOO)(CH(3)OH)].1.5CH(3)OH.H(2)O](n) (1), tetramer [Zn(4)(mu(2)-FcCOO)(6)(mu(4)-O)] (2), and coordination polymers [Pb(FcCOO)(mu(2)-FcCOO)(bpe)](n) (3) (bpe = 1,2-bis(4-pyridyl)ethene), [[Zn(FcCOO)(2)(bpt)].2.5H(2)O](n) (4) (bpt = N,N'-bis(3-pyridylmethyl)thiourea), and [Zn(FcCOO)(eta(2)-FcCOO)(bbp)](n) (5) (bbp = 4,4'-trimethylene-dipyridine). Compounds 1 and 2 are formed by ferrocenecarboxylate units coordinating with Pb(II) or Zn(II). In polymer 1, ferrocenecarboxylate units have four kinds of coordinate modes; just these novel coordinate modes lead to the unprecedented one-dimensional polymer where two kinds of rhomboids are arranged alternatively along the chain. Compound 2 is a tetramer, in which a distinct connectivity of the six ferrocene units is established through the four Zn atoms. Compounds 3-5 are obtained by organic ligands bridging Pb(II) or Zn(II), leading to a new type of metal-organic coordination polymer.     

溶液中芳香单酮的聚集态

本文对九种芳香单酮(苯乙酮、对氯苯乙酮、对甲氧基苯乙酮、对氨基苯乙酮、对硝基苯乙酮、间硝基苯乙酮、2.4-二甲基苯乙酮、1-萘乙酮和1-萘基苯基甲酮)在丙酮溶液中的吸收光谱进行了比较。发现芳香单酮在溶液中的分散是不均匀的, 随浓度增加, 有芳香单酮的聚集体生成。且芳香单酮分子的共轭体系越发达或苯环上电子云密度越犬, 分子就越易聚集。同时提出芳香单酮聚粲时的分子排列是苯环对苯环“面对面”取向的推断。     

Solid state synthesis and structure of two novel polyoxometalates [(n-Bu)4N]4[M6O19][Ag2I4](M?Mo,W)†

The reaction of [NH₄]₂[MO₂S₂], AgI and (n-Bu)₄NBr in solid state produced the polyoxometalates [(n-Bu)₄N]₄[M₆O₁₉][Ag₂I₄] (1, M? Mo; 2, M? W) which were structurally determined. The crystals of 1 and 2 are isomorphous, monoclinic, space group P2₁/c. 1, a = l.6624(2), b=1.6699(3), c=l.7217(2) nm, β=98.29(1)°, V=4.729(1) nm³, Z=2, R=0.040, R_w“0.037; 2, a = 1.6636(3), b = 1.6733(3), c = 1.7190(3) nm, β=98.25(1)°, V=4.736(l) nm³, Z = 2, R = 0.038, R_w = 0.047. The results of the structure determination showed that the two compounds had the same structures whose skeletons are composed of [Ag₂I₄]². and [M₆O₁₉]^2-. The difference of them and heteropolymetalate compounds synthesized in solution is that the title compounds contain cluster. ion, heteropolymetalate and organic cations, while the latter is only composed of heteropolymetalate and organic cations.     

Synthesis and biological activity of novel 2-(3-trifluoromethylphenoxy)-4-trifluoromethylthiazole-5-carboxamide derivatives

Novel 2-(3-trifluoromethylphenoxy)-4-trifluoromethylthiazole-5-carboxamides were designed and synthesized utilizing ethyl 3-amino-4,4,4-trifluoro-2-butenoate as a starting material via six steps. Subsequently, their biological activities were evaluated in the greenhouse. Results indicated that several compounds have some insecticidal or fungicidal activity at 600 g ai/ha and 300 g ai/ha, respectively.     

Unicyclic Graphs with Minimal Energy

If G is a graph and ₁,₂,..., _n are its eigenvalues, then the energy of G is defined as E(G)=|₁|+|₂|++| _n |. Let S _n ³ be the graph obtained from the star graph with n vertices by adding an edge. In this paper we prove that S _n ³ is the unique minimal energy graph among all unicyclic graphs with n vertices (n6).