Structure-property modelling of complex formation of strontium with organic ligands in water

The method of substructural molecular fragments based on representation of the molecular graph by ensembles of fragments and involving calculations of those contributions to the given property is applied to the modelling of stability constants of the complexes of strontium(II) with organic ligands in water. Reliability of predictions of developed structure-property models was examined using three different test sets of structurally diverse ligands. The obtained models have been used for generation and screening of combinatorial library of virtual ligands. Some hypothetical efficient Sr(II) binders were suggested.     

Theoretical prediction of the contact distance dependence of the electron transfer reactivity of the ClO/ClO− coupling system

On the basis of the structures and properties of the ClO/ClO^? system obtained at the density functional theory (DFT) (UB3LYP) level, employing the 6‐311+G(3df) standard basis set, the electron transfer reactivity of this system is investigated. The results indicate that there are five possible stable coupling complexes that correspond to the generous minima on the global potential energy surfaces (PES). The most stable coupling complex is planar EC4, in which there is a O? O linkage with two trans‐Cl atoms. Their stabilization energies are calculated to be 20.57 (EC1: C₁), 20.54 (EC2: C₂, ²B), 20.69 (EC3: C₁), 20.70 (EC4: C_s, ²A′), and 20.69 (EC.5: C_2h, ²B_u) kcal/mol at the B3LYP/6‐311+G(3df) level; with the correction of the basis set superposition error (BSSE), the stability order of these encounter complexes is EC4 > EC.5 > EC3 > EC1 > EC2. Based on the five encounter complexes, five coupling modes are designed for the study of the electron transfer reactivity of this system. The dissociation energy curves at the activated states and the corresponding activation energies of these five coupling modes are obtained and are compared at the B3LYP/6‐311+G(3df) and MP2/6‐311+G* levels. The inapplicability of DFT methods has also been discussed in this article in predicting the energy curves, especially with a long contact distance, in which DFT methods give the abnormal behavior for the dissociations of the complexes caused by the “inverse symmetry breaking” problem. On the basis of the golden rule of the time‐dependent perturbation theory, the electron transfer reactivity and the contact distance dependence of the various electron transfer kinetics parameters (e.g., activation energy, coupling matrix element) have been analyzed at the UMP2(full)/6‐311+G* level. The electron transfer can take place over a range of contact distances, but the most effective coupling distance corresponds to only a small range. The coupling orientation analyses also indicate that the most favorable coupling mode to the electron transfer does not always correspond to the most stable encounter complex mechanism. Some highly energetic coupling modes are more favorable for the electron transfer. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Synthesis and Crystal Structure of a New 2D Honeycomb-like Cadmium(II) Complex with Tripodal Ligand

ＩｎｔｒｏｄｕｃｔｉｏｎＩｎｔｈｅｐａｓｔｓｅｖｅｒａｌｙｅａｒｓ ,ｃｏｎｓｉｄｅｒａｂｌｅｐｒｏｇｒｅｓｓｈａｓｂｅｅｎａｃｈｉｅｖｅｄｉｎｃｏｎｔｒｏｌｌｉｎｇｔｈｅａｓｓｅｍｂｌｙｏｆｉｎｄｉｖｉｄｕａｌｂｕｉｌｄｉｎｇｂｌｏｃｋｓｉｎｔｏｓｔｒｕｃｔｕｒｅｓｗｉｔｈｓｐｅｃｉｆｉｃｔｏｐｏｌｏｇｉｅｓａｎｄｉｎｔｅｒｅｓｔｉｎｇｐｒｏｐｅｒｔｉｅｓｓｕｃｈａｓｍｏｌｅｃｕｌａｒｒｅｃｏｇｎｉｔｉｏｎ ,ｉｏｎｅｘｃｈａｎｇｅａｎｄｓｅｌｅｃｔｉｖｅｇｕｅｓｔｉｎｃｌｕｓｉｏｎ .1 3 Ｉｔｉｓ…     

SYNTHESIS AND CATALYTIC PROPERTY OF POLYSTYRENE SUPPORTED PHENYLALANINE SCHIFF BASE COMPLEX OF Mn（Ⅱ） IN AEROBIC OXIDATION OF CYCLOHEXENE

The polystyrene supported phenylalanine Schiff base complex of Mn(Ⅱ)(PS-Sal-Phe-Mn)was prepared with chloromethylated styrene polymer beads, 2,4-dihydroxybenzaldehyde,L-phenylalanine and manganese(Ⅱ)acetate tetrahyrate., The polymeric ligand and the complex were characterized by FT-IR,, small area X-ray photoelectron spectroscopy(XPS), and ICP-AES. In the presence of the manganese complex, cyclohexene(1)was effectively oxidized by molecular oxygen without reductant. The major products of the reaction were 2-cyclohexen-1-ol(2),2-cyclohexen-1-one(3)and 2-cyclohexen-1- hydroperoxide(4), which was different with typical oxidation of cyclohexene. The influence of reaction temperature and additive for oxidation had been studied. The selectivity of 2-cyclohexen-l-hydroperoxide varied with reaction time and different additives. The mechanism of cyclohexene oxidation had also been discussed.     

新型的含硫族元素碳硼烷配体的三(3，5-二甲基-1-吡唑)硼氢钼配合物的合成和分子结构(英)

三齿单核三(3，5-二甲基-1-吡唑)硼氢钼配合物Tp^*Mo(O)Cl₂ (1)(Tp^*=三(3，5-二甲基-1-吡唑)硼氢HB(C₃H(Me₂)N₂)₃)与含硫族元素碳硼烷的锂盐[(THF)₂LiE₂C₂B₁₀H₁₀(THF)]<     

Improvement of some pharmaceutical properties of nocloprost by β- and γ-Cyclodextrin Complexation

Inclusion complexation of nocloprost, a potent antiulcer prostaglandin derivative, with -, -, and -cyclodextrins (CyDs) in aqueous solutions has been studied by the solubility method and¹³C-NMR spectroscopy. The steric requirement of host-guest interaction was reflected in the magnitude of the stability constants and the thermodynamic parameters of the inclusion complexes. Solid complexes of nocloprost with - and -CyDs in a molar ratio of 1 : 2 were obtained on the basis of aBs-type phase solubility diagram. The X-ray diffraction data suggested that nocloprost is included in the cylindrical channel formed by coaxial alignment of -CyD molecules to give a channel type structure. Release and thermal behavior of the solid complexes was examined and compared with nocloprost itself. The results indicated that the -CyD complex may have great utility among the three CyDs, being a rapid dissolving form of nocloprost with improved thermal stability.     

Thermochemistry of interactions of Na+ with benzo-15-crown-5 ether in acetonitrile-water mixtures at 298.15 K

Enthalpies of dissolution of benzo-15-crown-5 ether (B15C5) in mixtures of acetonitrile with water and in solutions of NaI and NaBPh₄ (I=0.05 mol dm^–3) in these mixtures were measured at 298.15 K. From the obtained results and appropriate literature data, the thermodynamic functions of B15C5/Na⁺ complex formation in acetonitrile-water mixtures were determined. The enthalpies of transfer of the complex B15C5/Na⁺ from pure acetonitrile to the examined mixtures were calculated and are discussed.     

Zig‐Zag Diphosphene Oligomers Linked by Silver(I) Cation

The coordination of silver cation to diphosphene Mes*P=PMes* ( 1 , Mes* = ^tBu₃C₆H₂) was investigated in detail. The reaction of 1 with Ag[Al(OR_F)₄] (OR_F = OC(CF₃)₃) in the ratios of 2 : 1, 3 : 2 and 1 : 2 led to the formation of the first cationic silver linked diphosphene complexes 2 — 4 . Complexes 2 and 3 contain two and three diphosphene molecules linked by the linear Ag(I) cation, respectively, and they feature unusual zig‐zag topologies. Complex 4 is a dinuclear silver complex, and each Ag(I) center features a tetrahedral geometry, coordinated by one phosphorus atom of diphosphene 1 and three chloro atoms of two CH₂Cl₂ molecules.     

Diastereoselective addition of organolithiums to 1,3-oxazolidines complexed with aluminum tris(2,6-diphenylphenoxide) (ATPH)

1,3-Oxazolidines were easily obtained by condensation of N-substituted (R)-phenylglycinol with aldehydes. Addition of organolithium reagents to 1,3-oxazolidines by complexation with the bulky Lewis acid aluminum tris(2,6-diphenylphenoxide) (ATPH) readily produced the corresponding chiral amines with good yield and high diastereoselectivity. The configuration of the new stereogenic center was shown to be opposite to that of adducts obtained for the same 1,3-oxazolidines using Grignard reagents. The best diastereoselectivity was achieved using N-isopropyl-1,3-oxazolidines. The mechanism of addition was deduced by determining the stereochemistry of the iminium-aluminum complex by NOE experiments.     

Ferromagnetically coupled heterobinuclear Cu(Ⅱ)-Ln(Ⅲ) complexes with N,N''''-bis(2-aminoethyl)-oxamido dianion as a bridged ligand

Six novel μ-oxamido heterobinuclear complexes, namely Cu(oxae)Ln(Me2bpy)2-(ClO4)3 (Ln=La, Nd, Gd, Tb, Ho, Er), where oxae denotes N, N'-bis(2-aminoethyl)oxamido dian-ion, Me2bpy is 4,4'-dimethyl-2,2'-bipyridyl, have been synthesized and characterized by elemental analyses, IR, conductivity measurements and electronic spectra. The temperature dependence of the magnetic susceptibility of Cu(oxae)Gd(Me2bpy)2(ClO4)3 has been meaured over the range 4-300 K. The least-squares fit of the experimental susceptibilities yielded J - 1.87 cm-1.The observed Gd(Ⅲ)-Cu(Ⅱ) coupling is ferromagnetic. One plausible mechanism that can cause a ferromagnetic coupling between Gd(Ⅲ) and Cu(Ⅱ) is discussed in terms of spin-polarization.