Homolysis of the Ln-N (Ln = Yb, Eu) bond. Synthesis, structural characterization and catalytic activity of ytterbium(II) and europium(II) complexes with methoxyethyl functionalized indenyl ligands

The interaction of methoxyethyl functionalized indene compounds (C(9)H(6)-1-R-3-CH(2)CH(2)OMe, R =t-BuNHSiMe(2)(1), Me(3)Si (2), H (3)) with [(Me(3)Si)(2)N](3)Ln(mu-Cl)Li(THF)(3)(Ln=Yb (4), Eu (5)) produced a series of new ytterbium(II) and europium(II) complexes via tandem silylamine elimination/homolysis of the Ln-N (Ln=Yb, Eu) bond. Treatment of the lanthanide(III) amides [(Me(3)Si)(2)N](3)Ln(mu-Cl)Li(THF)(3)(Ln=Yb (4), Eu (5) with 2 equiv. of, 1,2 and 3, respectively, produced, after workup, the ytterbium(II) complexes [eta5:eta1-Me(2)Si(MeOCH(2)CH(2)C(9)H(5))(NHBu-t)](2)Yb(II) (6), (eta5:eta1-MeOCH(2)CH(2)C(9)H(5)SiMe(3))(2)Yb(II) (7), (eta5:eta1-MeOCH(2)CH(2)C(9)H(6))(2)Yb(II)(8) and the corresponding europium(II) complexes [eta5:eta1-Me(2)Si(MeOCH(2)CH(2)C(9)H(5))(NHBu-t)](2)Eu(II)(9), (eta5:eta1-MeOCH(2)CH(2)C(9)H(5)SiMe(3))(2)Eu(II)(10) and (eta5:eta1-MeOCH(2)CH(2)C(9)H(6))(2)Eu(II)(11) in moderate to good yield. In contrast, interaction of the corresponding indene compounds 1, 2 or 3 with the lanthanide amides [(Me(3)Si)(2)N](3)Ln (Ln = Yb, Eu) was not observed, while addition of 0.5 equiv. of anhydrous LiCl to the corresponding reaction mixture produced, after workup, the corresponding ytterbium(II) or europium(II) complexes. All the new compounds were fully characterized by spectroscopic and elemental analyses. The structures of complexes, and were determined by single-crystal X-ray analyses. The catalytic activity of all the ytterbium(II) and europium(II) complexes on MMA polymerization was examined. It was found that all the ytterbium(II) and europium(II) complexes can function as single-component MMA polymerization catalysts. The temperature, solvent and ligand effects on the catalytic activity were studied.     

Regioselective coupling of pentafluorophenyl substituted alkynes: mechanistic insight into the zirconocene coupling of alkynes and a facile route to conjugated polymers bearing electron-withdrawing pentafluorophenyl substituents

The reaction of Cp(2)ZrCl(2) with 2 equiv of BuLi at -78 degrees C, followed by the addition of an unsymmetrical tetra- or pentafluorophenyl substituted alkyne R(1)C[triple bond]CAr(f) (R(1), Ar(f) = (CH(2))(4)Me, p-C(6)F(4)H; Me, p-C(6)F(4)H; Ph, C(6)F(5)), resulted in regioselective couplings of these alkynes to zirconacyclopentadienes in which the Ar(f) substituents preferentially adopt the 3,4-positions (beta beta) of the zirconacyclopentadiene ring. With Cp(2)Zr(py)(Me(3)SiC[triple bond]CSiMe(3)) as the zirconocene reagent, the couplings could be carried out at room temperature; however, at higher temperatures significant quantities of the 2,4-fluoroaryl substituted (alpha beta) isomers were also formed. None of the conditions employed produced the 2,5-fluoroaryl substituted (alpha alpha) isomers. These fluoroaryl-substituted zirconacyclopentadienes were readily converted to butadienes via reactions with acids. The zirconacyclopentadiene Cp(2)ZrC(4)-2,5-Ph(2)-3,4-(C(6)F(5))(2), which resulted from the coupling of PhC[triple bond]C(C(6)F(5)), was converted to the corresponding thiophene by reaction with S(2)Cl(2), and to an arene by reaction with MeO(2)CC[triple bond]CCO(2)Me/CuCl. Mechanistic studies on zirconocene couplings of (p-CF(3)C(6)H(4))C[triple bond]C(p-MeC(6)H(4)) indicate that the observed regioselectivities are determined by an electronic factor that controls the orientation of at least one of the two alkynes as they are coupled. Additionally, these studies suggest an unsymmetrical transition state for the zirconocene coupling of alkynes, and this is supported by DFT calculations. The reaction of [(C(6)F(5))C[triple bond]CCH(2)](2)CH(2) with Cp(2)Zr(py)(Me(3)SiC[triple bond]CSiMe(3)) resulted in a zirconacyclopentadiene in which the pentafluorophenyl substituents have been forced into the 2,5-positions (alpha alpha). Zirconocene coupling of the diyne (C(6)F(5))C[triple bond]C-1,4-C(6)H(4)-C[triple bond]C(C(6)F(5)) provided a route to conjugated polymers bearing electron-withdrawing pentafluorophenyl groups.     

分散聚合水基聚苯胺乳胶微球制备与表征

水溶性空间稳定剂聚乙烯吡咯烷酮（PVP）存在时，采用分散聚合制备水溶性单分散的聚苯胺(PAn)乳胶粒子，采用透射电子显微镜（TEM）观察粒子形态及尺寸；利用紫外-可见吸收光谱对胶体分散体系进行表征.实验结果表明，当PAn含量较少（w< 16.78％）时， PAn-PVP复合乳胶粒子呈米粒状；当PAn含量较大（w >23.22％）时， PAn-PVP复合乳胶粒子呈球形.     

An efficient route for the preparation of a 21-fluoro progestin-16 alpha,17 alpha-dioxolane,a high-affinity ligand for PET imaging of the progesterone receptor

Two different synthetic routes were explored for the synthesis of fluoro furanyl norprogesterone (FFNP) 1, a high-affinity ligand for the progesterone receptor (PgR) that is being developed as a PET imaging agent for PgR-positive breast cancer. Both approaches proceed through a key intermediate, triol 5. The first approach, starting from keto-ketal 2, employed a dioxenyl group as a synthon for installing a corticosteroid side chain in keto-alcohol 4. The second approach, starting from propargylic acetate 12b, involved the application of a two-step method, a Pd(II)-catalyzed oxidative rearrangement followed by a base-catalyzed acetate rearrangement of the intermediate unsaturated acetate 13b, to generate the requisite corticosteroid side chain in keto-acetate 14b. This intermediate was further elaborated to the final product 1 via efficient dihydroxylation with potassium permangnate, furan acetalization with scandium triflate, and mesylation and fluorination reactions. The palladium-catalyzed route is considerably more efficient than the dioxene approach for the synthesis of key intermediate triol 5, and the scandium triflate-catalyzed acetalization, in particular, led to a considerable improvement in the overall yield of the endo furan acetal alcohol 16a. This route provides a major improvement in the overall yield of the final progestin target, FFNP 1.     

A Novel 3‐D Heterobimetallic Cyano‐bridged Coordination Polymer Incorporating Ag···Ag Interaction: [Cu(dien)Ag(CN)2]2[Ag2(CN)3][Ag(CN)2]

A three‐dimensional cyano‐bridged copper(II) complex, [Cu(dien)Ag(CN)₂]₂[Ag₂(CN)₃][Ag(CN)₂] ( 1 ) (dien = diethylenetriamine), has been prepared and characterized by X‐ray crystallography. Complex 1 crystallized in the monoclinic space group P2₁/n with a = 6.988(2), b = 17.615(6), c = 12.564(4) Å, β = 90.790(5)°. The crystal consists of cis‐[Cu(dien)]²⁺ units bridged by [Ag(CN)₂]^— to form a zig‐zag chain. The Ag atoms of the free and bridging [Ag(CN)₂]^— link together to form additional infinite zig‐zag chains with short Ag···Ag distances. The presence of Ag···Ag interactions effectively increases the dimensionality from a 1‐D chain to a 3‐D coordination polymer.     

Period-doubling and chaotic oscillations in the ferroin-catalyzed Belousov-Zhabotinsky reaction in a CSTR

The ferroin-catalyzed Belousov-Zhabotinsky(BZ) reaction,the oxidation of malonic acid by acidic bromate,is the most commonly investigated chemical system for understanding spatial pattern forma-tion. Various oscillatory behaviors were found from such as mixed-mode and simple period-doubling oscillations and chaos on both Pt electrode and Br-ISE at high flow rates to mixed-mode oscillations on Br-ISE only at low flow rates. The complex dynamic behaviors were qualitatively reproduced with a two-cycle coupling model proposed initially by Gy?rgyi and Field. This investigation offered a proper medium for studying pattern formation under complex temporal dynamics. In addition,it also shows that complex oscillations and chaos in the BZ reaction can be extended to other bromate-driven nonlinear reaction systems with different metal catalysts.     

聚对苯撑对苯二甲酰胺液晶的相态转变

本工作以H(?)ppler流变粘度计、退偏振光法及小角激光光散射法研究了聚对苯撑对苯二甲酰胺的浓硫酸溶液在不同浓度和温度下的粘性行为、光学性质和区域结构的变化,发现聚对苯撑对苯二甲酰胺的各向异性溶液在不同温度下呈现向列型液晶和胆甾型液晶特征,说明芳香聚酰胺的液晶体系与小分子液晶相类似,也具有多种中介相的转变现象。这里的中介相转变是由向列型转变为胆甾型,但不是直接的同时是一个单变性的相转变过程。     

SiO_2粒子对PMMA/SAN共混体系相分离行为的影响

采用小角激光光散射(SALLS)并结合动态流变学方法,考察了气相法二氧化硅(SiO2)粒子的加入对聚甲基丙烯酸甲酯/苯乙烯-丙烯腈无规共聚物(PMMA/SAN)共混体系相行为的影响,得到了添加SiO2粒子前后的相图,发现SiO2粒子对基体相行为的影响与基体的组成有关.对PMMA/SAN(60/40)体系,加入SiO2粒子后相分离温度上升,但并未改变相分离机理,仍为亚稳单相分解过程(spinodal decomposition,SD);而对于PMMA/SAN(30/70)体系,加入SiO2粒子后却降低了体系的相分离温度.该现象可能是SiO2粒子和基体组分界面间组成与PMMA/SAN共混物基体组成的差异造成的.     

含氨基酸侧链的有机硅高分子催化剂 ⅩⅤ.γ-(L-酪氨酰胺基)丙基硅氧烷钯催化剂的合成加氢活性及其结构表征

本文报导了四种不同N/Pd摩尔比的聚γ-(L-酪氨酰胺基)丙基硅氧烷钯催化剂的合成及其催化加氢活性,这类催化剂与聚γ-((L-酷氨酸)丙基硅氧烷钯催化剂相比较,虽然均具有类似的N→Pd配位的活性中心组成,但它们对底物的加氢活性则明显不同,前者对丙烯腈、丙烯酸、环己烯和1-癸烯的催化活性比后者高,对苯乙烯则相反。N/Pd摩尔比、反应温度、溶剂以及体系的pH值对催化活性的影响,两者的情况大致相同,标题催化剂对衣康酸的催化加氢,产物的光学纯度为30％。