Crystal Structures of Cs+-Crown Ether Complexes Containing Polynuclear Mercury Iodide Anions

Reactions of CsI and HgI₂ with benzo-15-crown-5 (B15C5) and 15-crown-5 (15C5) in an ethanol-acetone mixture produced [Cs(B15C5)₂]₂[Hg₂I₆] (1) and {[Cs(15C5)]₂[Hg₂I₆]}_n (2), respectively. The structures of the two complexes are quite different. Molar ratios of Cs⁺ : crown ether are 1 : 2 in 1 and 1 : 1 in 2. Complex 1 consists of two Cs(B15C5) ₂ ⁺ cations and a Hg₂I ₆ ^2- anion. Cs⁺ lies between the two crown-5 ligands, resulting in a sandwich-type cation. Cationic Cs(B15C5) ₂ ⁺ and anionic Hg₂I ₆ ^2- are linked together by electrostatic interactions and the complex 1 is an ion pair compound. Complex 2 consists of infinite [Cs(15C5)]₂[Hg₂I₆] units. Each structural unit contains two Cs(15C5)⁺ cations and a Hg₂I ₆ ^2- anion. Cs⁺ is coordinated by five oxygen atoms of 15C5, three iodine atoms of Hg₂I ₆ ^2- , and an iodine atom of Hg₂I ₆ ^2- in an adjacent structural unit. The interactions between the Cs⁺ of Cs(15C5)⁺ and an I^– in Hg₂I ₆ ^2- from adjacent structural units polymerize the complex 2, resulting in a one-dimensional network structure. The anions of Hg₂I ₆ ^2- in both complexes are similar. The two mercury atoms are linked through two bridging iodine atoms and each mercury is also coordinated by two terminal iodines. Crystal data for 1: space group P2₁/c (No. 14), a = 12.253(4), b = 20.945(7), c = 16.110(6) Å, = 111.0(1)°, V = 3860 ų, Z = 4, R = 0.082 (R _w = 0.089). Crystal data for 2: space group P2₁/c (No. 14), a = 12.157(4), b = 8.546(4), c = 20.666(6) Å, = 91.54(3)°, V = 2146 ų, Z = 4, R = 0.034 (R _w = 0.048).     

L—组氨酸和色氨酸三元体系中稀土（Ⅲ）,钙（Ⅱ）的化学形态

在模拟生理条件下（３７℃,Ｉ＝０．１５ｍｏｌ／ＬＮａＣｌ）,用ｐＨ电位滴定与计算机模拟计算相结合的方法研究了镨（Ⅲ）、钆（Ⅲ）、铽（Ⅲ）、镱（Ⅲ）４ｔｋｈ ｔｑｄ ｆｆｆｆｙｂ ｂｂ ｔ ｑｇｈ （Ⅱ）、锌（Ⅱ）离子在Ｌ－组氨酸、色氨酸三元体系中的化学形态。讨论了稀土（Ⅲ）、钙（Ⅱ）和锌（Ⅱ）的物种分布特点。     

葡萄糖、果糖和蔗糖在甲酰胺溶液中的体积性质

报导了含葡萄糖、果糖和蔗糖的甲酰胺溶液的密度数据，无限稀释表观摩尔体积和体积第二维里系数．利用改进的定标粒子理论、基团几何模型和基团加合方法，求解了溶质的空腔生成体积，溶质-溶剂间的氢键作用对体积性质的影响，并和水溶液中的情况进行了比较．     

钛硅沸石中的一种非活性钛物种

Synthesis of the titanium silicalite TS-1 was first reported by Taramasso et al[1]in 1983. TS-1 has received considerable interest during the last decade because of its unique catalytic properties in oxidation reactions involving H2O2 as the oxidant. It is accepted that the extraframework Ti species in TS-1 favor the decomposition of H2O2and should be avoided. But in the present study, it was observed that there was a kind of Ti species inactive in both the oxidation reaction and the decomposition of H2O2.     

聚全氟乙丙烯树脂中六氟丙烯分布问题的探讨

<正> 聚全氟乙丙烯树脂(以下简称FEP)是四氟乙烯与六氟丙烯的共聚物.目前对FEP尚无适当溶剂,所以不能用C~(3)高分辨NMR测定共聚单体在共聚物中的分布,故采用X射线衍射方法测量晶格常数和结晶度,以及密度与熔点的测定,对国产不同聚合体系FEP中的六氟丙烯分布问题进行探讨. 图1比较了聚四氟乙烯(PTFE)及FEP的X射线衍射谱(23℃)。在FEP共聚物中除了(100)晶面衍射峰外,尚有微弱的(110),(200)等晶面衍射峰,可以看出,FEP的行     

燕山海泡石的研究及其在C1化学中的应用(英文)

采用化学分析、ＸＲＤ、ＦＴＩＲ、ＤＴＡ、ＴＧＡ、ＳＥＭ、ＴＥＭ以及ＢＥＴ吸附等方法对燕山海泡石的物理化学性能进行了表征。选择了四个反应体系表征海泡石载体催化剂的催化性能,即二氧化碳加氢甲烷化、二氧化碳加氢合成低碳烯烃、甲烷化法挣化合成氨原料气和选择氧化反应。结果表明,海泡石载体催化剂的催化活性优于以氧化铝和二氧化硅为载体的传统催化剂的催化活性。     

吡啶酰胺基配体与Mn~(2 )、Fe~(3 )、Ru~(3 )配合物的合成和催化环己烯的氧化反应

由于吡啶环较一般芳环更稳定,抗氧化能力强,且毗院环上氮的孤电子对与中心金属的ｄ轨道通过配位作用可组成更大的共轭体系,增强了中心金属与配体之间电子云的流动性,从而可调节金属配合物与氧形成超氧、过氧或单氧活性物种的电子云分布（包括电荷分布）,进而影响其催化活性和选择性Ｕ,’１。根据这一构想,本文合成了含毗院酚胺基配体的金属Ｍｎ,Ｆｅ,Ｒｕ的配合物,在纯氧作氧源下,考察了它们催化环己烯氧化反应的性能。１催化剂的制备称取２０ｍｍｏｌＺ一毗陡甲酸溶于ｓｍｌ毗院中,１０ｍｍｏｌｌ,２一乙Ｍ胺（或１,个丁Ｍ胺…     

柚子皮衍生类蜂窝状碳材料在同步检测重金属离子中的应用

不含金属的碳材料通过廉价且易获得的柚子皮经KOH活化和高温热解获得,该碳材料具有高比表面积(1 055 m~2·g~(-1))和高石墨化程度的类蜂窝状结构。将多孔碳(PAC)材料修饰后的电极作为工作电极,采用阳极溶出伏安法(SWASV)同步检测Cd~(2+)、Pb~(2+)和Cu~(2+)离子,表现出较高的灵敏度、可重复性、稳定性和较低的检测限。研究认为PAC的微孔和中孔可以充当有效的离子传递通道,从而加速离子的扩散并显著提高交换效率,而高的石墨化程度提高了材料的导电性,加速了电子传输。     

Lutidine‐Based Chiral Pincer Manganese Catalysts for Enantioselective Hydrogenation of Ketones

A series of Mn^I complexes containing lutidine‐based chiral pincer ligands with modular and tunable structures has been developed. The complex shows unprecedentedly high activities (up to 9800 TON; TON=turnover number), broad substrate scope (81 examples), good functional‐group tolerance, and excellent enantioselectivities (85–98 % ee) in the hydrogenation of various ketones. These aspects are rare in earth‐abundant metal catalyzed hydrogenations. The utility of the protocol have been demonstrated in the asymmetric synthesis of a variety of key intermediates for chiral drugs. Preliminary mechanistic investigations indicate that an outer‐sphere mode of substrate–catalyst interactions probably dominates the catalysis.     

An All‐Alkynyl Protected 74‐Nuclei Silver(I)–Copper(I)‐Oxo Nanocluster: Oxo‐Induced Hierarchical Bimetal Aggregation and Anisotropic Surface Ligand Orientation

The hardness of oxo ions (O^2?) means that coinage‐metal (Cu, Ag, Au) clusters supported by oxo ions (O^2?) are rare. Herein, a novel μ₄‐oxo supported all‐alkynyl‐protected silver(I)–copper(I) nanocluster [Ag_74?xCu_xO₁₂(PhC≡C)₅₀] ( NC‐1 , avg. x=37.9) is characterized. NC‐1 is the highest nuclearity silver–copper heterometallic cluster and contains an unprecedented twelve interstitial μ₄‐oxo ions. The oxo ions originate from the reduction of nitrate ions by NaBH₄. The oxo ions induce the hierarchical aggregation of Cu^I and Ag^I ions in the cluster, forming the unique regioselective distribution of two different metal ions. The anisotropic ligand coverage on the surface is caused by the jigsaw‐puzzle‐like cluster packing incorporating rare intermolecular C?H???metal agostic interactions and solvent molecules. This work not only reveals a new category of high‐nuclearity coinage‐metal clusters but shows the special clustering effect of oxo ions in the assembly of coinage‐metal clusters.