固—液界面阴离子集团构型的密度泛函理论研究

通过键合不同数量的H2PO4^-离子构造了H4P2O8^2-和H4P4O16^8-两种阴离子集 团。利用密度泛函理论对它们的构型进行优化并计算其振动频率和喇曼散射效率。 测量了固—液界面边界层的喇曼光谱并与理论计算结果进行对比分析，进一步研究 了阴离子集团的结构、聚合及脱水等过程。实验和理论研究均表明阴离子二聚体是 KDP晶体的生长基元，他们在固液界面将进一步形成多聚体分子集团，而离子集团 的脱水过程则发生在距KDP晶体表面约50μm的固—液界面边界层中。随着生长层向 界面的推进，这些分子集团将变得越来越有序。本文的研究结果对确定晶体生长界 面动力学过程、发展和完善晶体生长理论有重要意义。     

Platinum carbonyl derived catalysts on inorganic and organic supports: a comparative study

Fumed silica, silica gel, silica-alumina and cross-linked (5.5%) polystyrene have been functionalized with quaternary ammonium groups and the Chini cluster [Pt₁₂(CO)₂₄]²⁻ has been anchored onto these functionalized materials by ion pairing. A catalyst has also been prepared by the adsorption of Na₂[Pt₁₂(CO)₂₄] on unfunctionalized fumed silica. The catalytic activities of the resultant materials, and that of commercially purchased 5% platinum on alumina have been studied for the hydrogenation of a variety of unsaturated compounds. The substrates studied are: α-acetamidocinnamic acid, cyclohexanone, acetophenone, methyl pyruvate, ethyl acetoacetate, nitrobenzene and benzonitrile. Compared to the polystyrene supported catalyst, the inorganic oxide supported catalysts have higher surface areas and for most of the substrates have notably higher activities. The functionalized fumed silica-based catalyst gives higher conversions than functionalized silica gel and silica-alumina-based catalysts. In the hydrogenation of acetophenone and ethyl acetoacetate, the functionalized fumed silica-based catalyst show superior activity compared to the commercial platinum catalyst, and the catalyst made by conventional adsorption method. In benzonitrile hydrogenation with all the cluster-derived catalysts a hydrazine derivative is selectively formed, but when the commercial platinum catalyst is used benzyl amine is the main product.     

磷脂液相二次离子质谱分析中的分子离子簇

对3种极性头不同的磷脂DMPG、DMPC、DMPE的液相二次离子质谱分析中出现 的分子离子簇现象进行了系统的研究。结果表明，虽然分子离子簇的形成与许多因素有关， 如PH值、离子强度等，但起决定作用的是样品在底物中的浓度，浓度增大有利于分子离子簇 的形成。研究还发现，由不同种类磷脂分子形成的分子离子簇峰明显高于由同种磷脂分子所 形成的分子离子簇峰，指出异种磷脂分子间的簇离子形成能力高于同种磷脂分子。此外还讨 论了磷脂分子在离子源条件下的稳定性、裂解规律及相互作用等。结果表明，本实验所选用 的磷脂分子在LSIMS条件下是稳定的，均能得到较强的分子离子峰，其主要碎片峰是磷酰键断裂而产生的碎片离子峰。     

活泼配盐[(μ-RE)(μ-E′)Fe_2(CO)_6][Et_3NH][E,E′=S,Se]的亲电反应研究——蝶状Fe_2SSe及Fe_2Se_2簇合物的合成及表征

本文由［（μｔＢｕＳ）（μＣＯ）Ｆｅ２（ＣＯ）６］［Ｅｔ３ＮＨ］和硒粉形成的［（μｔＢｕＳ）（μＳｅ）Ｆｅ２（ＣＯ）６］［Ｅｔ３ＮＨ］，分别与溴化苄，二碘甲烷及邻一、间一、对一双（溴甲基）苯反应，合成了蝶状Ｆｅ２ＳＳｅ单簇物（μｔＢｕＳ）（μＰｈＣＨ２Ｓｅ）Ｆｅ２（ＣＯ）６（３ａ）和双簇物［（μｔＢｕＳ）Ｆｅ２（ＣＯ）６］２（μＳｅＺＳｅμ）［Ｚ＝ＣＨ２，ｏ．ｍ．ｐ双（亚甲基）苯］（４ａｄ）。类似地，由［（μＰｈＳｅ）（μＣＯ）Ｆｅ２（ＣＯ）６］［Ｅｔ３ＮＨ］和硫粉或硒粉所形成的［（μＰｈＳｅ）（μＳ）Ｆｅ２（ＣＯ）６］［Ｅｔ３ＮＨ］或［（μＰｈＳｅ）（μＳｅ）Ｆｅ２（ＣＯ）６］［Ｅｔ３ＮＨ］分别与对一双（溴甲基）苯反应合成了蝶状Ｆｅ２ＳＳｅ和Ｆｅ２Ｓｅ２双簇物［（μＰｈＳｅ）Ｆｅ２（ＣＯ）６］２［μＳ（ｐＣＨ２Ｃ６Ｈ４ＣＨ２）Ｓμ］（５ａ）及［（μＰｈＳｅ）Ｆｅ２（ＣＯ）６］２［μＳｅ（ＰＣＨ２Ｃ６Ｈ４ＣＨ２）Ｓｅμ］（５ｂ）。所有产物均经元素分析、ＩＲ和１ＨＮＭＲ表征。     

(AB)8(AB=BN，AlP，GaAs，InSb)团簇环状结构与性质的密度泛函理论研究

用杂化密度泛函B3LYP方法研究了(AB)₈(AB=BN，AlP，GaAs，InSb)团簇环形结构的平衡几何构型、电子结构、振动特性以及极化率。计算结果表明，(AB)₈团簇的双层环状结构中，每个A(B)原子都与3个B(A)原子成键，且Ⅴ族元素的原子比Ⅲ族元素的原子更接近团簇中心，(BN)₈、(AlP)₈、(GaAs)₈、(InSb)₈的平均极化率依次增大，IR和Raman谱峰发生红移。另外，讨论了热力学稳定性和动力学稳定性的变化。     

Chloroaqua Complexes [M3S4(H2O)9?xClx](4?x)+ (M = Mo, W; x = 4, 6, 7) and Their Supramolecular Compounds with Cucur[8]uril

Compounds of trigonal cluster chloroaqua complexes with cucurbit[8]uril were synthesized by slowly evaporating HCl solutions of chalcogenides heterometallic cubane cluster complexes of molybdenum and tungsten with cucurbit[8]uril in air; the complexes were characterized by X-ray diffraction analysis: (H₃O)₈[Mo₃S₄(H₂O)_2.5Cl_6.5]₂Cl(PdCl₄)·(C₄₈H₄₈N₃₂O₁₆)· 29H₂O (a = 13.3183(17) Å, b = 13.7104(18) Å, c = 18.225(3) Å; α = 80.263(3)°, β = 77. 958(3)°, γ = 87.149(4)°, V = 3207.4(7) ų, space group P , Z = 1, ρ(calc) = 1.900 g/cm³), (H₃O)₄ [Mo₃S₄(H₂O)₃Cl₆]₂·(C₄₈H₄₈N₃₂O₁₆)₃·68H₂O (a = 21.413(6) Å, c = 49.832(10) Å; γ = 120°, V = 19788(8) ų, space group R , Z = 3, ρ(calc) = 1.695 g/cm³), (H₃O)₆ [Mo₃S₄(H₂O)₃Cl₆]₂Cl₂·(C₄₈H₄₈N₃₂O₁₆)·12H₂O (a = 15.881(2) Å, b = 17.191(2) Å, c = 23.276(4) Å; β = 98.865(15)°, V = 6278.7(15) ų, space group P2₁/c, Z = 2, ρ(calc) = 1.638 g/cm³), [W₃S₄(H₂O)₅Cl₄]₂·(C₄₈H₄₈N₃₂O₁₆)₃·35H₂O (a = 21.038(3) Å; α = 61.20(1)°, V = 6762.0(14) ų, space group R , Z = 1, ρ(calc) = 1.582 g/cm³). The [Mo₃S₄(H₂O)₃Cl₆]²⁻ anion complex was isolated as three geometrical isomers.Original Russian Text Copyright © 2004 by E. V. Chubarova, D. G. Samsonenko, H. G. Platas, F. M. Dolgushin, A. V. Gerasimenko, M. N. Sokolov, Z. A. Starikova, M. Yu. Antipin, and V. P. Fedin__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 1049–1058, November–December, 2004.     

The "invisible" 13C NMR chemical shift of the central carbon atom in [(Ph3PAu)6C]2+: a theoretical investigation

The experimental 13C NMR chemical shift of the central carbon atom in the octahedral [(Ph3PAu)6C]2+ cluster was investigated on the basis of relativistic density functional calculations. In order to arrive at independent model conclusions regarding the value of the chemical shift, a systematic study of the dependence of the cluster structure on the phosphine ligands, the chosen density functionals, and the basis set size was conducted. The best structures obtained were then used in the NMR calculations. Because of the cage-like cluster structure a pronounced deshielding of the central carbon nucleus could have been expected. However, upon comparison with the 13C NMR properties of the related complex [C{Au[P(C6H5)2(p-C6H4NMe2)]}6]2+, Schmidbaur et al. have assigned a signal at delta=135.2 ppm to the interstitial carbon atom. Our calculations confirm this value in the region of the aromatic carbon atoms of the triphenylphosphine ligands. The close-lying signals of the 108 phenyl carbon atoms can explain the difficulties of assigning them experimentally.     

含氮宾或卡宾的金属羰基簇合物的结构化学研究——Ⅰ.H_2Fe_3(N-C_6H_5)(CO)_9和Fe_3(N-C_6H_5)(μ_3-CO)(CO)_9的合成和结构

含氮宾的两个三核羰基铁簇合物是由[Et_3NH][HFe_3(CO)_(11)]与C_6H_5NCO在苯中反应获得。应用四园衍射仪测定了H_2Fe_3(N-C_6H_5)(CO)_9(Ⅰ)和Fe_3(N-C_6H_5)(μ_3-CO)(CO)_9(Ⅱ)的晶体结构。晶体数据为:C_(15)H_7NO_9Fe_3(Ⅰ),空间群P2_1/a,a=18.343(2),b=9.072(1),c=11.451(1)(?),β=102.03(1)°,V=1863.7(?)~3,Z=4,D_c=2.143g/cm~3;C_(16)H_5NO_(10)Fe_3(Ⅱ),空间群P2_1/c,a=8.634(1),b=13.026(1),c=17.642(2)(?),β=97.68(1)°,V=1966.3(?)~3,Z=4,D_c=1.820g/cm结构系用直接法解出,最后R_(Ⅰ)因子为0.033,R_(Ⅱ)因子为0.027。测定结果表明,(Ⅰ)和(Ⅱ)分子均具有C_s对称性,且三个Fe原子共面,呈近似等边三角形结构。(Ⅰ)中面桥N原子以不对称方式与三个Fe原子成键;(Ⅱ)中面桥羰基以不对称方式与三个Fe原子键连。Fe-N和Fe-C键长分别在1.896-1.938(?)和2.006-2.110(?)之间。     

C_πB~-的激光等离子体产生与质谱分析

随着“足球烃”C_(60)及其他“球碳烃”的发现,以及对它们奇妙的结构与化学行为的不断揭示,碳原子簇的产生与研究已成为当前化学界的一个热门课题.Smalley等最近又将C_(60)中的一个碳原子以硼原子取代,成为Lewis酸,使这方面的研究更加深入。近二年来,我们在自制的装置上对碳原子簇的结构作了较为充分的研究后,又以独特的方式产生了链状构型的C_nB~-,记录了它们的负离子质谱。     

Research on Reactivities of MoCluster． A Selective Substitution Reaction of the Bridging（dtp） Ligand and Structure of Tetranuclear Molybdenum Cluster Compound ［Mo_4S_4（μ－O_2CC_6H_5）_2（dtp）_4］

ＲｅｓｅａｒｃｈｏｎＲｅａｃｔｉｖｉｔｉｅｓｏｆＭｏＣｌｕｓｔｅｒ．ＡＳｅｌｅｃｔｉｖｅＳｕｂｓｔｉｔｕｔｉｏｎＲｅａｃｔｉｏｎｏｆｔｈｅＢｒｉｄｇｉｎｇ（ｄｔｐ）ＬｉｇａｎｄａｎｄＳｔｒｕｃｔｕｒｅｏｆＴｅｔｒａｎｕｃｌｅａｒＭｏｌｙｂｄｅｎｕｍＣ...