Cyclopentadienylcobalt Complexes Containing Two Phosphine Ligands

The ionic complexes [C₅H₅Co(L)(Ph₂PMe)I]⁺ [I]^- (L = Ph₃P and Ph₂PMe) were prepared by the reactions of cyclopentadienyl(triphenylphosphine)cobalt and cyclopentadienyl(methyldiphenylphosphine)cobalt diiodides with methyldiphenylphosphine. The treatment of these complexes with sodium tetraphenylborate results in the formation of [C₅H₅Co(L)(Ph₂PMe)I]⁺[BPh₄]^- compounds.     

含C^N-螯合配体的环戊二烯基铱抗癌配合物

合成、表征了8个半三明治结构环戊二烯基金属铱配合物[（η⁵-Cp^x）Ir（C^N）Cl],其中Cp^x分别为四甲基环戊二烯基（C₅Me₄H）,五甲基环戊二烯基（Cp^*）,四甲基（苯基）环戊二烯基（Cp^xph）,四甲基（联苯）环戊二烯基（Cp^xbiph）,C^N为苯亚甲基甲胺（BIMA）,N-（4-甲氧基苯亚甲基）苯胺（MBIA）。测定了其中3个配合物的单晶结构。所有配合物对Hela人宫颈癌细胞显示出很强的细胞毒性,IC₅₀值为1.7~32.9 μmol·L^-1。经检测Cp^x铱配合物的抗癌活性顺序为Cp^xbiph > Cp^xph > C₅Me₄H > Cp^*。配合物[（η⁵-Cp^xbiph）Ir（BIMA）Cl] （A4）和[（η⁵-Cp^xbiph）Ir（MBIA）Cl] （B4）表现出了最高的抗癌活性,比临床铂类药物顺铂活性高4倍以上。经检测,铱配合物A1~B4不与9-甲基腺嘌呤和9-乙基鸟嘌呤反应,与pBR322 DNA也没有作用,但这些配合物能够作为氢转移催化剂,将辅酶NADH转化为NAD⁺。机理研究表明IC₅₀浓度的配合物A4、B4处理Hela细胞时会引起明显的细胞凋亡和细胞周期的变化,并大幅增加细胞内活性氧（ROS）的水平。     

含C^N-螯合配体的环戊二烯基铱抗癌配合物

合成、表征了8个半三明治结构环戊二烯基金属铱配合物[（η⁵-Cp^x）Ir（C^N）Cl],其中Cp^x分别为四甲基环戊二烯基（C₅Me₄H）,五甲基环戊二烯基（Cp^*）,四甲基（苯基）环戊二烯基（Cp^xph）,四甲基（联苯）环戊二烯基（Cp^xbiph）,C^N为苯亚甲基甲胺（BIMA）,N-（4-甲氧基苯亚甲基）苯胺（MBIA）。测定了其中3个配合物的单晶结构。所有配合物对Hela人宫颈癌细胞显示出很强的细胞毒性,IC₅₀值为1.7~32.9 μmol·L^-1。经检测Cp^x铱配合物的抗癌活性顺序为Cp^xbiph > Cp^xph > C₅Me₄H > Cp^*。配合物[（η⁵-Cp^xbiph）Ir（BIMA）Cl]（A4）和[（η⁵-Cp^xbiph）Ir（MBIA）Cl]（B4）表现出了最高的抗癌活性,比临床铂类药物顺铂活性高4倍以上。经检测,铱配合物A1~B4不与9-甲基腺嘌呤和9-乙基鸟嘌呤反应,与pBR322 DNA也没有作用,但这些配合物能够作为氢转移催化剂,将辅酶NADH转化为NAD⁺。机理研究表明配合物A4、B4处理Hela细胞时会引起明显的细胞凋亡和细胞周期的变化,并大幅增加细胞内活性氧（ROS）的水平。     

Half-sandwich 1,3-Di-t-butylcyclopentadienyl Rhodium Complexes Containing Sulfido Ligands

Interest in the coordination chemistry of organo-transition metal complexescontaining sulfur ligands is continuing because they are involved in important catalyticprocesses[1 ,2 ] ,particularly hydrodesulfurization and hydrogenation reactions[3] and theyundergo a variety of reaction with metal species[4～ 6] . Although half-sandwichpentamethylcyclopentadienyl complexes with sulfido ligands are well known,only threetypes of half-sandwich compounds with chelating oligosulfido ligands have beendes…     

Transition Metal Complexes Containing Functionalized Organoimido and Phosphaneiminato Ligands

Two different types of modified imido and phosphaneiminato ligands are investigated, namely chelate ligands and redox‐functionalised ligands. The first examples of di(organoimido)chromium as well as di(phosphaneiminato)titanium and niobium chelates are described. Furthermore, the first complexes containing redox‐functionalised organoimido ligands are presented, together with the first structurally characterised redox‐functionalised phosphaneiminato complex. Compounds of the type [(RN)₂M(CH₂Ph)₂] (M = Cr, Mo) are used as catalysts for the (co‐)polymerisation of the polar olefins methyl methacrylate, acrylonitrile and vinyl acetate. A range of X‐ray crystal structure determinations provide clear evidence for the quantum‐chemical result that, similar to organoimido complexes, the potential energy well for the angle at the nitrogen atom is very shallow for phosphaneiminato complexes.     

Manganese Containing Heterometallic Clusters Containing Ligands Derived from Elements of Groups 15 and 16

The area of manganese-containing mixed-metal clusters is reviewed. Discussion is divided into two sections: that containing clusters bridged by ligands derived from elements of Group 15 and those containing ligands derived from the Group 16 elements of the Periodic Table. Emphasis is given to synthetic strategies and those reactivity features which result in Mn-containing new cluster formations. Dedicated to Professor Dr. Dieter Fenske on the occasion of his 65th birthday. Yuri V. Torubaev is on leave from the N.S. Kurnakov Institute of General and Inorganic Chemistry, Leninskii Prospeckt, Moscow, Russia     

PEEK–WC-Based Mixed Matrix Membranes Containing Polyimine Cages for Gas Separation

Membrane-based processes are taking a more and more prominent position in the search for sustainable and energy-efficient gas separation applications. It is known that the separation performance of pure polymers may significantly be improved by the dispersion of suitable filler materials in the polymer matrix, to produce so-called mixed matrix membranes. In the present work, four different organic cages were dispersed in the poly(ether ether ketone) with cardo group, PEEK-WC. The m-xylyl imine and furanyl imine-based fillers yielded mechanically robust and selective films after silicone coating. Instead, poor dispersion of p-xylyl imine and diphenyl imine cages did not allow the formation of selective films. The H₂, He, O₂, N₂, CH₄, and CO₂ pure gas permeability of the neat polymer and the MMMs were measured, and the effect of filler was compared with the maximum limits expected for infinitely permeable and impermeable fillers, according to the Maxwell model. Time lag measurements allowed the calculation of the diffusion coefficient and demonstrated that 20 wt % of furanyl imine cage strongly increased the diffusion coefficient of the bulkier gases and decreased the diffusion selectivity, whereas the m-xylyl imine cage slightly increased the diffusion coefficient and improved the size-selectivity. The performance and properties of the membranes were discussed in relation to their composition and morphology.     

Computation of the Number of Isomers of Coordination Compounds Containing Identical Monodentate Ligands and Chelating Ligands

This paper outlines a simple method of counting the number of isomers of coordination compounds containing identical monodentate ligands and chelating ligands.     

Synthesis of Novel Macrocyclic Ligands Containing Phosphoryl and Aminoacetal Fragments

Abstract

A method for the synthesis of novel phosphorylated aminoacetals was developed. The latter are involved in Mannich reaction as amine component with calix[4]resorcinol and formaldehyde to form tetrasubstituted macrocycles containing four acetal groups and four phosphonate (phosphine oxide) fragments on the “upper” rim of molecule with high yields.     

Synthesis of New Bidentate Phosphine Ligands Containing Saturated Phosphorus Heterocycles

The synthesis of two ethylene-bridged bidentate phosphines is described. 1,2-Bis(1-phospholano)ethane ((C(4)H(8))PCH(2)CH(2)P(C(4)H(8))) was synthesized by the stepwise addition of 2,2-dioxo-1,3,2-dioxathiepane to H(2)PCH(2)CH(2)PH(2). 1,2-Bis(1-phosphorinano)ethane ((C(5)H(10))PCH(2)CH(2)P(C(5)H(10))) was synthesized by the novel photochemical addition of 1,4-pentadiene to H(2)PCH(2)CH(2)PH(2). These bis(phosphines) form two-to-one complexes of the form Fe(PP)(2)Cl(2) when added to iron(II) chloride.     

The Synthesis and Characterization of Some New Thioether-Imidazole Containing Ligands

Procedures are described involving a convenient condensation of 4(5)-hydroxymethylimidazole or 5-methyl-4-hydroxymethyliraidazole with several thiols. The main step, the condensation reaction in refluxing acetic acid, is essentially the same for all ligands.     

Synthesis and Characterization of Heteropoly Coordination Compounds Containing Optical Ligands

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Self-Assembly of Benzimidazole-Derived Tris-NHC Ligands and AgI-Ions to Hexanuclear Organometallic Cages and Their Unusual Transmetalation Chemistry

Multi-ligand self-assembly to attain the Ag^I-N-heterocyclic carbene (NHC)-built hexanuclear organometallic cages of composition [Ag₆( 3 a , b )₄](PF₆)₆ from the reaction of benzimidazole-derived tris(azolium) salts [H₃- 3 a , b ](PF₆)₃ with Ag₂O was achieved. The molecular structures of the cages were established by X-ray diffraction studies along with NMR and MS analyses. The existence of a single assembly in solution was supported by diffusion-ordered spectroscopy (DOSY) ¹H NMR spectra. Further, transmetalation reactions of these self-assembled complexes, [Ag₆( 3 a , b )₄](PF₆)₆, with Cu^I/Au^I-ions provided various coinage metal-NHC complexes having diverse molecular compositions, which included the first example of a hexanuclear Cu^I-dodecacarbene complex, [Cu₆( 3 b )₄](PF₆)₆.