Crystal Structure of Complex Tris(4,4,4-trifluoro-1-phenyl-1,3-butanedione)(1,10-phenanthroline) Europium(III)

IntroductionCertainlanthanideionspossessharpemissionlinesinthevisibleregions.Thepossibilityoftransferringenergyeffi cientlytotheseionsbywayofstronglyabsorbingtransitionscharacteristicoforganicligandshasspurredmanyworkerstoinvestigatelanthanidechelatesaspotentiallasermaterials .Amongthemtheternarycomplexesofeuropium(III)andter bium(III)withtris(β diketonates)andanneutralligandhaveespeciallyattractedmuchattentionfortheirstronglumi nescence.Itmakethemaextensiveapplicationsindevelop mentofnewl…     

卟啉试剂与贵金属高灵敏显色反应的研究 Ⅴ.Ru(Ⅲ)-T(4-AOP)P-TritonX-100体系

本文研究了在Ｃｄ（Ⅱ）和ＴｒｉｔｏｎＸ－１００存在下，ｍｅｓｏ－四（４－乙酰氧基苯）卟啉［Ｔ（４－ＡＯＰ）Ｐ］与钌（Ⅲ）的显色反应。结果表明，在ｐＨ９．７～１０．３介质中，Ｒｕ（Ⅲ）与Ｔ（４－ＡＯＰ）Ｐ形成了灵敏度很高的稳定络合物，其表观摩尔吸光系数为７．０４×１０５Ｌ·ｍｏｌ－１·ｃｍ－１。钌浓度在０～１．２μｇ／１０ｍＬ范围内服从比尔定律。络合物的摩尔比为Ｒｕ（Ⅲ）∶Ｔ（４－ＡＯＰ）Ｐ＝１∶１。在掩蔽剂存在下，方法有一定的选择性，应用于合成试样中钌的测定，结果满意。     

荧光法研究金属络合物与脱氧核糖核酸的相互作用

研究了Tb(phen) 2 Cl3 ·H2 O·CH3 CH2 OH与小牛胸腺脱氧核糖核酸 (DNA)的作用方式 ,结果表明 :它们之间的作用存在两种模式 :嵌入与静电作用。运用Tb(phen) 2 Cl3 ·H2 O·CH3 CH2 OH作荧光探针初步研究了Ni(phen) 3 (ClO4) 2 ·3H2 O的两种手性对映体与DNA的相互作用 ,结果表明 :这两种对映体的作用存在差别     

Host-guest complexes of cucubit[8]uril with phenanthrolines and some methyl derivatives

Cucurbituril a molecular container (or host) has a rigid hollow interior cavity which is large enough to accommodate, one or more, smaller molecules (or guests). The cavity is accessible through two carbonyl portal openings. Molecules or guests enter the …     

Nickel-Ruthenium Mixed-Metal Carbonyl Clusters Syntheses and Solid State Structures of the Two Tetrahedral Clusters [PPh4][NiRu3(μ3 H)(CO)9(μ-CO)3] and [NEt4]2[NiRu3(CO)8(μ-CO)4]

Redox condensation of [Ru₃H(CO)₁₁]- with Ni(CO)₄, in tetrahydrofuran solution, under a nitrogen atmosphere, yields the tetranuclear anion [NiRu_H(CO)₁₁)-. Subsequent deprotonation with Bu'OK in acetonitrile solution leads to the formation of the related dianion. Both anions have been characterized by spectroscopic techniques, elemental analysis and single crystal X-ray diffraction. [PPh₄][NiRu₃H(CO)₁₂] crystallizes in the triclinic space group PI with unit cell dimensionsof a = 11.842(2) Å,b = 12.335(3) Å, c = 13.3080) Å,a = 91.89(2)°, = 93.35(1)°,y = 96.41(2)°, Z = 2, V= 1926.9(7) Å'. The NiRu₃, metal core of the molecule defines a distorted tetrahedron with nine terminal and three edge bridging carbonyl groups. The hydrido ligand was located by difference Fourier techniques and was found to bridge the NiRu₂ basal triangle at a distance of 0.88(6) A from this plane. Selected average distances and angles are: Ru-Ru = 2.839 Å, Ru-Ni = 2.640 Å, Ru-C, = 1.910 A,Ru-C _b = 2.084 Å, Ni-C _b = 2.022 Å, Ru-H = 1.77 Å, C-0, = 1.135 Å, C-O _b = 1.159 Å, M-C-O, = 176.3°,M-C--O _b = 139.3°;other distances are: Ni-C₁ = l.758(7) Å, Ni-H= 1.85(7) Å. [NEt₄]₂[NiRu₃(CO)₁₂] crystallizes in the orthorhombic space group Pnma (no. 62) with unit cell dimensions ofa=20.247(5) Å,b = 15.038(4)Å,c = 12.079(3) Å, Z=4, V=3678(2) A'. The molecule contains a tetrahedral NiRu₃ core with eight terminal and four edge bridging carbon monoxide groups which bridge the three Ni-Ru and one Ru-Ru bond. Average distances and angles are: Ru -Ru =2.3050A Ru-Ni 2.648 Å, Ru-C _t = 1.878 Å, Ru-C _b 2.045 Å, Ni-C _b = 2.055 Å, C-O _t = 1.145 Å, C-01,=1.157 Å, M-C-O,= 176.9°, M-C-O _b = 138.6°; other distance is: Ni-C _t = 1.754(10) Å,t = terminal,b = bridging.     

Molecular and crystal structures of ruthenium and osmium arene clusters

The molecular and crystal structures of a number of ruthenium and osmium clusters of nuclearity between three and six containing arene fragments such as C₆H₆, C₆H₃Me₃, C₆H₄Me₂ and C₆H₅Me have been investigated. Attention has been focused on the relationship between the terminal ( ⁶-coordination) and face-capping ( ₃: ²: ²: ²-coordination) bonding modes. Empirical packing potential energy calculations have been employed to investigate the intermolecular organization in the crystal. It has been shown that the arene fragments in mono-arene clusters form ribbons, while in bis-arene clusters graphitic-like interactions throughout the crystal are established. The factors controlling the ease of arene reorientational motion in the solid state has also been investigated in relation to the shape, size and geometry of the molecules and of their interlocking modes.     

锰（Ⅱ）—邻菲口罗啉配合物极谱吸附波及其应用

在ｐＨ９．５ＮＨ３ＮＨ４Ｃｌ缓冲溶液中，Ｍｎ（Ⅱ）与邻菲口罗啉形成的配合物在－１．３６Ｖ（ｖｓ．ＳＣＥ）处产生一灵敏的吸附波，一阶导数峰电流与Ｍｎ（Ⅱ）浓度在５×１０－８５×１０－６ｍｏｌ／Ｌ范围内呈线性关系，检出限为２×１０－８ｍｏｌ／Ｌ对极谱性质及反应机理进行了研究，用该法测定了大豆和茶叶中的微量锰，结果满意     

Synthesis, characterization, and reactivity of half-sandwich Ru(II) complexes containing phosphine, arsine, stibine, and bismutine ligands

The synthesis and some reactions of the Ru(II) and Ru(IV) half-sandwich complexes [RuCp(EPh₃)(CH₃CN)₂]⁺ (E=P, As, Sb, Bi) and [RuCp(EPh₃)(η³-C₃H₅)Br]⁺ have been investigated. The chemistry of this class of compounds is characterized by a competitive coordination of EPh₃ either via a RuE or a η⁶-arene bond, where the latter is favored when the former is weaker, that is in going down the series. Thus in the case of Bi, the starting material [RuCp(CH₃CN)₃]⁺ does not react with BiPh₃ to give [RuCp(BiPh₃)(CH₃CN)₂]⁺ but instead gives only the η⁶-arene species [RuCp(η⁶-PhBiPh₂)]⁺ and [(RuCp)₂(μ-η⁶,η⁶-Ph₂BiPh)]²⁺. Similarly, the EPh₃ ligand can be replaced by an aromatic solvent or an arene substrate. Thus, the catalytic performance of [RuCp(EPh₃)(CH₃CN)₂]⁺ for the isomerization of allyl-phenyl ethers to the corresponding 1-propenyl ethers is best with E=P, while the conversion drops significantly using the As and Sb derivatives. By the same token, only [RuCp(PPh₃)(CH₃CN)₂]⁺ is stable in a non-aromatic solvent, whereas both [RuCp(AsPh₃)(CH₃CN)₂]⁺ and [RuCp(SbPh₃)(CH₃CN)₂]⁺ rearrange upon warming to [RuCp(η⁶-PhEPh₂)]⁺ and related compounds. In addition, the potential of [RuCp(EPh₃)(CH₃CN)₂]⁺ as precatalysts for the transfer hydrogenation of acetophenone and cyclohexanone has been investigated. Again aromatic substrates are clearly less suited than non-aromatic ones due to facile η⁶-arene coordination leading to catalyst's deactivation.     

Ruthenium-catalyzed one-pot hydroformylation of alkenes using carbon dioxide as a reactant

A new hydroformylation of alkenes using carbon dioxide as a reactant is shown to take place in the presence of ruthenium cluster complexes and halide salts. Similar or even better yields of alcohols were formed as compared to the conventional hydroformylation with CO under the same reaction conditions. The reaction proceeded in three steps: CO₂ is first converted to CO; then it is used as a reagent for hydroformylation to give aldehyde; subsequently, it is hydrogenated to alcohol. ESI-mass spectrometric analyses of the reaction solutions indicated formation of four kinds of ruthenium anionic complexes including tetra-, tri-, and mononuclear species. On the basis of experimental findings, possible roles of these complexes are discussed.     

How to Control the Chemoselectivity of the Catalytic Formation of Chiral γ-Lactams or 2,3-Disubstituted Pyrroles by the Choice of Solvent

Summary. The reaction of the unsaturated imine methyl(3-phenylallylidene)amine with ethylene and carbon monoxide in the presence of catalytical amounts of Ru₃(CO)₁₂ leads to the formation of two heterocyclic products. One of the products is a chiral γ-lactam, the other one a 2,3-disubstituted pyrrole derivative, in which only the carbon atom from carbon monoxide is incorporated. The selectivity in the formation of the products may be controlled by the choice of solvent. In general, in nonpolar solvents the formation of the lactam is preferred whereas the use of more polar solvents enhances the yield of the pyrrole. For most of the solvents used there is a linear dependence of the product ratio on the relative permittivity of the corresponding solvent. Typically, polar aprotic solvents do not follow this rule.