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).     

A study of PBT/PC blends by modulated DSC and conventional DSC

Two poly(butylene terephthalate)/polycarbonate (PBT/PC) blends with different formulations were analyzed by modulated DSC (MDSC) and conventional DSC to determine differences in crystallization behavior. A significant difference (30°C in cold crystallization temperature) between the two samples was detectable by MDSC while no significant difference was seen by conventional DSC. That indicatesthe total heat flow from MDSC is not always equivalent to the heat flow from conventional DSC as we have assumed or seen before. The reason has not been fully understood, but may be related to unusual nucleation and crystallization induced by modulation. Alternative conventional DSC methods were developed and compared to the MDSC results.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthdayThe authors like to thank Drs. Bernhard Wunderlich and Robert Gallucci for helpful discussion, David Shaker and Mary Parsonage for some DSC experiments. Technical support from TA Instruments is also greatly appreciated.     

Theoretical study of the local structure and Raman spectra of CaO-SiO2 binary melts

A procedure for the Raman spectra calculation of vitreous and molten silicates was presented in this paper. It includes molecular dynamics MD simulation for the generation of equilibrium configurations, Wilson's GF matrix method for the calculations of eigenfrequencies and corresponding vectors, electro-optical parameters method (EOPM) for the Raman intensity calculations, and the bond polarizability model (BPM) for the determination of polarizability and polarizability derivative. One of the most important characteristics of this procedure is the achievement of the partial Raman spectra of five tetrahedral units, as well as the total spectral envelope. In this paper, the calculation was carried out for the vitreous and molten calcium silicates with different compositions and at various temperatures. It is worthwhile to note that the calculation is based on statistical configurations distribution in the space and so it is not needed to artificially adjust the full width at half maximum (FWHM) of spectra. It was also tested through the good agreement of the calculated spectra with the experimental, including some regularity of spectral properties. According to the calculation, the symmetrical stretching of whole tetrahedral units, to which the stretching of Si-O(nb) bond gives the main contribution to intensity, is proven to be the dominance in the high-frequency range (800-1200 cm(-1)) and the symmetrical bending of Si-O(b)-Si, to which the stretching of Si-O(b) bond exhibits the main contribution, is the dominance in the medium-frequency range (400-700 cm(-1)). As the first theoretical results, the Raman scattering coefficient of each Q(i) was found little change along with the variation of composition and temperature.     

微波辐照下无皂阳离子聚(St-MMA)高分子纳米粒子的制备和表征

讨论了微波辐照下 ,以丙酮 水为分散介质 ,利用阳离子型自由基引发剂偶氮二异丁基脒盐酸盐(AIBA)引发苯乙烯 (St)和甲基丙烯酸甲酯 (MMA)共聚 ,合成出表面带正电荷的P(St MMA)共聚物纳米粒子 ,考察了丙酮用量、单体和引发剂浓度对纳米粒子粒径、粒径分布和乳液稳定性的影响 .结果表明 ,丙酮 水的体积比由 0增加到 1 2 6∶1时 ,粒子的平均水化半径从 12 2 2 1nm降低到 2 4 6 8nm ,粒径分布变宽 ,乳液抗电解质稳定性逐渐增强 ;增加引发剂和共聚单体MMA的浓度 ,粒子的水化半径逐渐减小 ,粒径分散系数增大 .     

Unexpected differences in the alpha-halogenation and related reactivity of sulfones with perhaloalkanes in KOH-t-BuOH

Most alkyl phenyl sulfones are readily alpha-chlorinated with CCl(4) and alpha-brominated with CBrCl3 in KOH-t-BuOH via radical-anion radical pair (RARP) reactions. While isopropyl mesityl sulfone (4) is easily alpha-chlorinated with CCl(4), it was completely recovered when treated with the more reactive CBrCl3. Subsequent investigations showed the latter result to be due to the poor acidity of 4 together with the rapid depletion of CBrCl3 and KOH by their reaction with each other, and led to a variety of other important results. 4-Hydroxyphenyl isopropyl sulfone (6) is unreactive with either CCl4 or CBrCl3 in KOH-t-BuOH, its phenoxide anion strongly reducing the electronegativity of the sulfonyl group, thereby inhibiting alpha-anion formation. This effect is reversed by the electron-withdrawing influence of two alpha-phenyls, so that benzhydryl 4-hydroxyphenyl sulfone (8) is readily alpha-halogenated in KOH-t-BuOH with CCl4 or CBrCl3. On further contact with KOH-t-BuOH the alpha-halogenated sulfones from 8 are decomposed into benzophenone and phenol. While the alpha-halogenated derivatives of 4-methoxyphenyl benzhydryl sulfone (9) are stable to base, they are decomposed even under mildly acidic conditions into 4-methoxyphenyl 4-methoxybenzenethiolsulfonate (9c), phenol, and benzophenone. Mono-alpha-halogenation of benzyl phenyl sulfone (10) enhances the rate of the subsequent halogenation, so that alpha,alpha-dihalogenation is attained while much substrate is still present and the mono-alpha-halogenated product is not detected. The ease of reductive debromination of alpha-bromo sulfones with Cl3C- was correlated with the stability of the formed alpha-anions, explaining the success with alpha-bromobenzylic sulfones but failure with alpha-bromoalkyl sulfones. In the presence of air and the absence of competing halogenation, formation of the alpha-anions of alkyl aryl sulfones is quickly accompanied by oxidative cleavage by atmospheric O2, leading to the formation of arenesulfonyl alcohols, arenesulfonyl halides, and haloarenes.     

New reactions of 1-alkynes catalyzed by transition metal complexes

Recently discovered catalytic reactions with ruthenium and lanthanide metal complexes have extended the scope of 1-alkynes as useful reagents. The specific formation of aryl-substituted (Z)-1,3-enzymes via the dimerization of HC(triple bond) CR(1) (R(1) = aryl) has been attained using dimeric lanthanide complexes, the catalytic activity of which appears to be unaffected by time. The dimerization of HC(triple bond) CR(2) (R(2) = t-Bu, SiMe(3)) catalyzed by Ru(cod)(cot)/PR(3) or RuH(2)(PPh(3))(3) produces a good yield of butatrienes (Z)R(2)CH=C=C=CHR(2) with a high degree of selectivity. Under certain conditions, HC(triple bond) C=SiMe(3) dimerizes to yield exclusively (Z)-M(3)Si-C(triple bond) C-CH=CH-SiMe(3). The hydration of HC(triple bond)CR(3) (R(3) = alkyl, aryl) catalyzed by RuCl(2)/PR'(3) or CpRuCl(PR"(3))(2) has realized the first example of anti-Markovnikov regioselectivity in an addition reaction of water that produces aldehydes R(3)CH(2)bond;CHO. The application of this reaction to propargylic alcohols has lead to their formal isomerization to alpha,beta-unsaturated aldehydes. In contrast, the addition of amines R(4)bond;NH(2) (R(4) = aryl) to HCtbond;CR(5) (R(5) = alkyl, aryl) conforms to Markovnikov's rule to produce ketimines R(5)bond;(C=NR(4))bond;CH(3) when catalyzed by a Ru(3)(CO)(12)/additive. Since the reaction can be performed in air without the need for any solvents, it enables the practical synthesis of aromatic ketimines, which are difficult to prepare by conventional methods. The synthesis of indoles using deactivated anilines is one practical application of this reaction. The mechanisms of some of these reactions have been analyzed in detail with the aid of theoretical calculations.