草酰胺桥联双核铜配合物金属胶束催化BNPP水解的动力学和机理研究

合成了草酰胺桥联双核铜配合物(RCu2(H2O)2(ClO4)2)(A)和(R′Cu2(H2O)2(ClO4)2)(B)。研究了A、B与表面活性剂LSS和CTAB形成的金属胶束催化二(对硝基苯酚)磷酸二酯(BNPP)水解机理,建立了动力学模型。结果表明在25℃、pH=7的条件下,该类金属胶束对BNPP水解有催化作用,BNPP催化水解速率比其自水解速率提高1×106倍,这是由于双核铜配合物中两个铜离子的协同作用、表面活性剂胶束的浓聚效应和pH效应所致。因此含双水的草酰胺桥联双核铜配合物金属胶束是一较好的磷酸二酯水解酶的模拟模型。     

Schiff碱Co(Ⅱ)配合物在胶束中催化BNPP水解

合成和表征了两种对称的带冠醚环或吗啉环的Schiff碱Co(Ⅱ)配合物,将此配合物和表面活性剂形成的金属胶束,用于模拟水解金属酶催化BNPP水解。通过分析反应体系的特性吸收光谱,提出了BNPP催化水解反应的机理,据此建立了金属胶束催化BNPP水解的动力学数学模型。本文还讨论了配合物结构、反应体系温度以及胶束对催化BNPP水解的影响。     

冠醚化Schiff 碱配合物金属胶束催化BNPP水解动力学

研究了两种新的冠醚化Schiff 碱过渡金属配合物与表面活性剂Brij35(聚氧乙烯(23)十二烷基醚)形成的金属胶束对BNPP（对硝基苯酚磷酸二酯）的催化水解反应. 探讨了催化反应机理, 建立了一种金属胶束催化BNPP水解的动力学数学模型; 计算了模拟酶催化反应的相关参数和表观活化能. 结果表明, 此类金属胶束作为模拟水解金属酶对BNPP水解反应表现出良好的催化活性.     

草酰胺桥联双核铜配合物金属胶束催化PNPA水解反应动力学

研究了草酰胺桥联双核铜配合物和不同表面活性剂胶束组成的金属胶束催化PNPA水解的动力学特征。结果表明：金属胶束催化PNPA水解为双分子反应；不同配体结构的配合物的催化活性不同；三种不同类型表面活性剂胶束对催化PNPA水解的影响也不同。     

双Schiff碱过渡金属配合物在胶束溶液中催化BNPP水解的研究

双Schiff碱过渡金属配合物和胶束形成的金属胶束作为模拟磷酸二酯水解酶用于催化BNPP水解，探讨了催化作用机理；提出了一种金属胶束催化BNPP水解的动力学数学模型。研究表明，本文所用的金属胶束在适当酸度、温度、介质的条件下对催化BNPP水解具有较高的活性。     

金属胶束催化: 二氧环胺Ni(Ⅱ)配合物催化羧酸酯水解

 合成了单核二氧大环四胺镍(Ⅱ)配合物,对该配合物在不同胶束体系中催化对硝基苯基α-吡啶甲酸酯(PNPP)的水解进行了动力学研究,用三元复合物动力学模型处理得到了相关的动力学和热力学参数. 结果表明,该配合物对PNPP水解反应有显著的催化作用,配合物在两性离子表面活性剂正月桂酸肌氨酸钠(LSS)和非离子表面活性剂聚氧乙烯(23)十二烷基醚(Brij35)胶束溶液中对PNPP水解的催化活性高于在阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)胶束溶液中的催化活性; 配合物的空间构型对反应速率有较大影响,具有四面体结构的配合物更有利于PNPP的水解.     

三乙醇胺-Co（Ⅱ）金属胶束催化4-硝基苯酚乙酸酯水解反应

本文分别研究了在有和无CTAB及Triton x-100两种表面活性剂存在时,三乙醇胺-Co(Ⅱ)配合物催化4-硝基苯酚乙酸酯(PNPA)水解反应动力学,实验结果表明,三乙醇胺-Co(Ⅱ)配合物对PNPA水解有较强的催化作用,与金属配合物键合的水分子离解所产生的活性物种ML-OH-是金属配合物催化水解PNPA的主要因素。表面活性剂胶束的存在对金属配合物催化水解PNPA有加速作用,这种加速作用主要是由于胶束的存在增大了与配合物键合的水分子的酸离解常数,从而使活性物种的数量增加所致。建立了催化反应的动力学数学模型,获得了催化反应相关的热力学和动力学参数。     

金属胶束模拟过氧化氢酶的热动力学研究

本文以金属胶束作为过氧化氢酶的模拟模型化合物，利用热动力学半寿期法分别研究了Fe^Ⅲ-trien金属配合物和Fe^Ⅲ-trien配合物分别与CTAB、SDS、Brij35等表面活性剂形成的金属胶束催化过氧化氢分解反应的热动力学。实验结果表明：Fe^Ⅲ-trien金属配合物与CTAB形成的金属胶束对过氧化氢分解反应有催化作用，而与SDS和Brij35形成的金属胶束对反应有禁阻作用。     

含肟基的钴和铜双核金属配合物催化磷酸二酯水解

本文合成了双核铜（II）和钴（II）配合物,并用动力学方法研究了它们对双-（对硝基苯基）磷酸二酯（BNPP）水解的催化活性。实验结果表明,单去质子化的肟基可以作为反应过程中的分子内亲核剂。双核铜（II）配合物比与其具有相似结构的单核配合物催化底物水解的活性高很多的事实表明,在双核配合物作催化剂的体系中很可能包含两个金属中心的双路易斯酸催化的机理。     

异双核配合物金属胶束模拟磷酸酯酶催化磷酸单酯水解

 合成和表征了四种含过渡金属离子Cu(Ⅱ)和Ni(Ⅱ)的草酰胺桥联异双核配合物,并将这些配合物与Brij35表面活性剂胶束构成金属胶束作为金属水解酶模拟物用于催化对硝基苯酚磷酸单酯(NPP)水解. 研究了金属胶束对NPP水解反应的催化机理,建立了异双核配合物催化NPP水解的动力学数学模型. 结果表明,四种草酰胺桥联异双核配合物在NPP水解反应中表现出较高的催化活性,随着胶束溶液pH的增大,配合物催化NPP水解的速率提高. 配合物中的两个金属离子在催化NPP水解过程中表现出较好的协同效应.     

Synthesis and Structural Characterization of Cu（pic）2[CO（NH2）2]2 and （picH2）2[Cu（pic）2（SCN）2]

1 INTRODUCTION The picolinic acid (picH), also called pyridine- 2-carboxylic acid, has a broad spectrum of physio- logical effects on the activity functions of both ani- mal and plant organisms. It is attributed increasing interest due to its ability to …     

Crystal structure of (C2H7N4O)2[(UO2)2)(OH)2(C2O4)(CHO2)2]

An X-ray diffraction study of the single crystals of (C₂H₇N₄O)₂[(UO₂)₂(OH)₂(C₂O₄)(CHO₂)₂] was carried out. The compound crystallizes in the triclinic system, space group $P\bar 1$ , Z = 2, a = 5.5621(8) Å, b = 8.1489(10) Å, c = 11.8757(16) Å, α = 88.866(7)°, β = 82.204(6)°, γ = 87.378(6)°, V = 532.7(1) ų, ρ_calcd = 2.988 g/cm³. The main structural units in the crystal are the [(UO₂)₂(OH)₂(C₂O₄)(CHO₂)₂)]^2? chains corresponding to the crystal chemical group A₂M ₂ ² K⁰²M ₂ ¹ (A = UO ₂ ²⁺ , M² = OH^?, K⁰² = C₂O ₄ ^2? , M¹ = CHO ₂ ^? ) of uranyl complexes. The chains are united into a three-dimensional framework through the electrostatic interaction and hydrogen bonds involving uranyl, oxalate, and hydroxyl groups, formate ions, and 1-carbamoylguanidinium cations.     

Rhodium-catalyzed dehydrocoupling of the sterically encumbered phosphine-borane adduct tBu(2)PH.BH(3): synthesis of the linear dimers tBu(2)PH-BH(2)-tBu(2)P-BH(3) and tBu(2)PH-BH(2)-tBu(2)P-BH(2)Cl

The dehydrocoupling of the sterically hindered phosphine-borane adduct tBu(2)PH.BH(3) above 140 degrees C is catalyzed by the rhodium complexes [Rh(1,5-cod)(2)][OTf] or Rh(6)(CO)(16) to give the four-membered chain tBu(2)PH-BH(2)-tBu(2)P-BH(3) (1), which was isolated in 60% yield and characterized by multinuclear NMR spectroscopy, mass spectrometry, and elemental analysis. Thermolysis of 1 in the temperature range 175-180 degrees C led to partial decomposition and the formation of tBu(2)PH.BH(3). When the dehydrocoupling of tBu(2)PH.BH(3) was performed in the presence of [[Rh(mu-Cl)(1,5-cod)](2)] or RhCl(3) hydrate, the chlorinated compound tBu(2)PH-BH(2)-tBu(2)P-BH(2)Cl (2) was formed which could not be obtained free of 1. The molecular structures of tBu(2)PH.BH(3), tBu(2)PH-BH(2)-tBu(2)P-BH(3) (1), and tBu(2)PH-BH(2)-tBu(2)P-BH(2)Cl (2) together with 1 were determined by single-crystal X-ray diffraction studies.     

The bivalent metal hypophosphites Sr(H2PO2)2, Pb(H2PO2)2 and Ba(H2PO2)2

The structures of isomorphous monoclinic strontium and lead bis­(di­hydrogenphosphate), Sr(H₂PO₂)₂ and Pb(H₂PO₂)₂, and orthorhombic barium bis­(di­hydrogen­phos­phate), Ba(H₂PO₂)₂, consist of layers of hypophosphite anions and metal cations exhibiting square antiprismatic coordination by O atoms. The Sr and Pb atoms are located on sites with point symmetry 2, and the Ba atoms are on sites with point symmetry 222. Within the layers, each anion bridges four metal cations.     

Infinite Three-Dimensional Coordination Polymers: Synthesis and Structures of [Cd (4,4''-bpy)2 (H2O)2]n (pic)2n, [Zn (4,4''-bpy)2 (H2O)2 ]n-(pic)2n (H2O)2n, and [Zn (4,4''-bpy)2 (H2O)2]n (4,4''-bpy)n (H2O)n (pic)2n

Recently, a new research realm in crystal engineering of supramolecular architecturesassembled by means of coordinate covalent bonding', hydrogen bonding', or other weakintermolecular interactions= has been rapidly expanding in order to rationally developnew classes of functional materials with cavities or pores. These types of compoundsmay exhibit interesting topological structures and the clathrations of the cavity structuresmay have many potential properties such as catalysis', electrical co…     

(CF3)2PAsH2 und (CF3)2AsAsH2

(CF₃)₂PAsH₂ and (CF₃)₂AsAsH₂ (CF₃)₂PAsH₂ is obtained in yields between 30 and 60% according to eq. (1) (CF₃)₂AsAsH₂ is formed by the analogous reaction with (CF₃)₂AsI, but is not sufficiently stable to be isolated. Both compounds are decomposed according to eq. (2) (CF₃)₂PAsH₂ can be studied in solution below ?40°C; it is characterized by molar mass determination and by its n.m.r. spectra (¹H, ¹⁹F, ³¹P). Reactions with polar [HBr, (CH₃)₂AsH, (CH₃)₂PN(CH₃)₂] and nonpolar [Br₂, As₂(CH₃)₄] reagents proceed by cleavage of the P? As bond.