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981.
The Pd-catalyzed annulation of arynes by 2-halobiaryls and related vinylic halides provides a very efficient, high yielding synthesis of polycyclic aromatic and heteroaromatic hydrocarbons. This process appears to involve the catalytic, stepwise coupling of two very reactive substrates, an aryne and an organopalladium species, to generate excellent yields of cross-coupled products. 相似文献
982.
Rate constants (k's) of the thermal cyclodimerization of ten meta-substituted trifluorostyrenes (m-Y-TFS's) have been measured in the temperature range 110–160°C. On the basis of these k's and the σmb values derived from 19F NMR data the spin-delocalization substituent constant σ˙m values of these ten meta-substituents have been calculated. The averaged σ˙m values are: m-Et, 0.09; m-t-Bu, 0.11; m-F, 0.03; m-Cl,?0.05; m-Br, 0.12: m-CF3, ?0.07; m-OMe, 0.10; m-NO2, ?0.002; m-CN, 0.11 and m-CO2Me, 0.08. Both the smallness of these values and the nonexistence of correlation between Hammett-Type polar σX and these σ˙m values support our belief that the σj?J approach is reliable and trustworthy. 相似文献
983.
采用穆斯堡尔谱及X光衍射法研究了共沉淀法制备的不同Fe/Mn比催化剂在焙烧、合成气还原及FT反应后体系相结构的变化。结果表明:锰助剂的加入使催化本相由铁磁性逐渐转化为超顺磁性,相应使催化剂还原逐渐难,Mn助剂促进了FT合成反应进行。反应性能与Fe/Mn尖晶石(Fe1-yMny)3O4组成含量及式中y大小密切相关,与MnCo3及MnO的存在也有一定关系。富铁催化剂中Mn主要起电子助剂作用,而富锰催化 相似文献
984.
甲烷在Mo/HZSM-5催化剂上的脱氢聚合反应 总被引:1,自引:0,他引:1
对不同Mo含量的Mo/HZSM-5催化剂的结构进行了表征,并对这些催化剂的甲烷非氧气氛下的转化反应进行了考察.催化剂的BET比表面积及酸性随Mo含量的增加而降低,当Mo含量大于5%时,Mo对ZSM-5分子筛的晶型有影响,并出现MoO3物相.甲烷在700℃时可高选择性地生成苯和乙烯,最佳Mo含量大约为2%.纯的MoO3或HZSM-5上该反应几乎不进行,因此,可能是分散的钼氧离子和分子筛的酸中心是甲烷转化的活性中心,只有二者的协同作用才能促进甲烷的转化.反应后催化剂中的钼物种被还原了.催化剂上的积炭可能是催化剂失活的主要原因之一,烧炭后催化剂活性基本恢复. 相似文献
985.
The solvent composition induced reentrant behavior of poly(N-isopropylacrylamide) (PNIPAM) chains grafted on a SiO2 surface in water-methanol mixtures was investigated using a quartz crystal microbalance with dissipation monitoring (QCM-D) at 20 degrees C. The frequency and energy dissipation responses showed that the grafted PNIPAM chains sharply collapse when the methanol content (x(m)) reaches approximately 17 mol %. In the range 17-50 mol %, the grafted chains remain in a collapsed state. Further increase of the methanol content leads to an abrupt reswelling of the collapsed chains at x(m) > approximately 50 mol %. The sharp reentrant swelling-to-collapse-to-swelling transition was attributed to the water-methanol complexation instead of the preferential adsorption effect. Our results also suggest that the water-methanol complexation is not induced by hydrophobic interaction but by hydrogen bonding. 相似文献
986.
Growth of porous single-crystal Cr2O3 in a 3-D mesopore system 总被引:1,自引:0,他引:1
Jiao K Zhang B Yue B Ren Y Liu S Yan S Dickinson C Zhou W He H 《Chemical communications (Cambridge, England)》2005,(45):5618-5620
Single-crystal Cr2O3 with regular mesopores has been synthesized using mesoporous silica KIT-6 as a template and characterized by using XRD, HRTEM and nitrogen adsorption/desorption. 相似文献
987.
Xiao-jun Wang Li Zhang Yibo Xu Dhileepkumar Krishnamurthy Chris H. Senanayake 《Tetrahedron letters》2004,45(38):7167-7170
A practical protocol for synthesis of 2-(N-substituted)-aminobenzimidazoles was developed. N-(2-Aminoaryl)thioureas undergo a CuCl-promoted intramolecular cyclization to give the corresponding 2-(N-substituted amino)benzimidazoles in good to excellent isolated yields. 相似文献
988.
Labile rhizosphere soil solution fraction for prediction of bioavailability of heavy metals and rare earth elements to plants 总被引:5,自引:0,他引:5
A labile rhizosphere soil solution fraction has been recommended to predict the bioavailability of heavy metals and rare earth elements to plants. This method used moist rhizosphere soil in combination with a mixture of 0.01 mol L(-1) of low-molecular-weight organic acids (LMWOAs) as extractant. The extracted soil solutions were fractionated into two colloidal fractions of <0.45 microm (F(3)) and <0.2 microm (F(2)), and one truly dissolved fraction including free metal ions and inorganic and organic complexes (fractionr(0.2 microm, LMWOAs) approximately r(0.45 microm, LMWOAs). In the case of rare earth elements the good correlation was obtained for both the wheat roots and shoots. Generally, the correlation coefficients obtained by LMWAOs were better than that obtained by the first step of BCR method. Therefore, LMWAOs and F(lrss) were strongly recommended to predict the bioavailability of metals in soil pools to plants. 相似文献
989.
990.
We report herein a novel coordination solid, [(DB24C8)Na][Cd(SCN)3] (6) (DB24C8 denotes dibenzo-24-crown-8), which exhibits a new type of [Cd(SCN)3-]infinity chain with two unusual stereochemical characteristics: (1) a mer-CdN3S3 coordination and (2) a linear Cd chain with a Cd...Cd...Cd angle of 180 degrees. In addition, the [(DB24C8)Na]+ monocation adopts a new structural type-a coiled structure-for the combination of crown ether DB24C8 and alkali metal Na+. The title compound crystallizes in a monoclinic unit cell of C2/c space group symmetry with lattice parameters a = 16.110(8) A, b = 20.380(5) A, c = 11.01(1) A, beta = 119.87(3) degrees, and Z = 4. The arrangement of the [Cd(SCN)3-](infinity) chains in the crystal lattice in the title compound is approximately hexagonal, creating triangular channels which are filled with [(DB24C8)Na]+ monocations. It was previously reasoned by us that the coiled [(DB24C8)Na]+ monocation, which lacks inversion or mirror symmetries, should enhance the tendency for the formation of the noncentrosymmetric space group of the title crystal, making it a potential second-order nonlinear optical crystal. Interestingly, however, the title compound crystallizes in a centrosymmetric space group (C2/c) and gives rise to no second harmonic generation (SHG). Previously known [Cd(SCN)3-](infinity) chains adopt fac-CdN3S3 coordination and a zigzag Cd chain configuration with a Cd...Cd...Cd angle of 165 degrees. The zigzag chains can align in either parallel or antiparallel fashion, resulting in efficient or no SHG effects, respectively. The linear Cd.Cd.Cd chain configuration observed in the title compound, on the other hand, makes it indistinguishable between parallel and antiparallel alignments. It is concluded that, to ensure the formation of noncentrosymmetric space groups, it is necessary to employ optically pure chiral cations as spacers and/or controllers. Furthermore, to enhance the nonlinear optical responses, [Cd(SCN)3-]infinity chains with fac-CdN3S3 coordination and parallel alignments of the zigzag Cd chains should be used. 相似文献