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81.
Complexes of Vanadium and Titanium with Salicylaldehyde benzoylhydrazone and 2-(2′-Hydroxyphenyl)-8-quinolinol. Crystal Structure of μ-Oxo-bis[oxo{2-(2′-hydroxyphenyl)-8-quinolinato(2-)}-vanadium(V)] . By reaction of titanium(IV)-isopropoxide and bis(acetylacetonato)-oxovanadium(IV) with salicylaldehyde benzoylhydrazone and 2-(2′hydroxyphenyl)-8-quinolinol, respectively, the metal complexes of the tridentate diacidic ligands were synthesized and characterized mass spectrometrically. The mass spectra of the titanium compounds correspond to the expected bisligand complexes whereas several species are demonstrable in the case of vanadium. Crystals of μ-oxo-bis[oxo{2-(2′-hydroxyphenyl)-8-quinolinolato(2-)}-vanadium(V)] were isolated and characterized by X-ray structural analysis. The complex exhibits C2 symmetry, accordingly the μ2-oxygen atom is situated on the 4 axis. The VOV bridge is angular with the unusually small bond angle of 107.3°. The coordination polyhedron is distorted octahedral. The compound additionally contains one molecule of chloroform per formula unit which is disordered in two positions. Crystallographic data see “Inhaltsübersicht”. 相似文献
82.
[Ni(H2O)6][Cu3Cl8(H2O)2] · (15-crown-5)2 · 2H2O can be conveniently prepared by the interaction of NiCl2 · 6H2O, CuCl2 · 2H2O and 15-crown-5 in water. The X-ray crystal structure reveals an ionic complex involved in a hydrogen-bonded two dimensional network with the [Ni(H2O)6]2+ and [Cu3Cl8(H2O)2]2− ions sandwiched between the 15-crown-5 macrocycles. The magnetic susceptibility data (4–300 K) and magnetisation isotherms (2–5.5 K; 0–5 T) are best interpreted in terms of intra-trimer ferromagnetic coupling within the [Cu3Cl8(H2O)2]2− moieties, with J ∼ 6 cm−1, and antiferromagnetic coupling between the trimers, the latter mediated by H-bonding pathways. Comparisons are made to other reported quaternary ammonium salts of [Cu3Cl8]2− and [Cu3Cl12]6−, most of which display structures that involve close stacking of such Cu(II) trimers, rather than being of the present isolated, albeit H-bonded, types. 相似文献
83.
Maria Bocheska Maria Hoffmann Urszula Lesiska Emilia Luks Wanda Radecka-Paryzek 《Tetrahedron》2005,61(52):12307-12313
New compounds: 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(3-diisopropoxyphosphorylpropoxy)calix[4]arene (1) and 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(3-methoxyethoxyphosphorylpropoxy)calix[4]arene (2) were synthesized and their ionophoric properties in ion-selective membrane electrodes were studied in comparison with already described by us 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(3-diethoxyphophorylpropoxy)calix[4]arene (3). Complexes of 1 with calcium(II), lanthanum(III), europium(III) and gadolinium(III) nitrates were prepared in direct reaction of the ligand and appropriate metal salts. They were characterized by spectral data (IR, UV/Vis, luminescence, NMR, ESI-MS) and elemental analysis. The similarity in complexing behavior of the (dialkoxyphosphoryl)propoxy-calix[4]arenes toward calcium and some lanthanides was observed. 相似文献
84.
The complexes Ln(NO3)3(OPCy3)3(EtOH)x (Cy = cyclohexyl, C6H11x = 0 for Ln = Eu, Er, x = 0.5 for Ln = La, Nd and x = 1 for Ln = Tm, Yb) have been prepared by reaction of lanthanide nitrates with Cy3PO in ethanol. The single crystal X-ray structures for Ln = La, Nd, Eu, Er, Tm and Yb are reported. The structures for Ln = La–Eu have two molecules in the unit cell in which the nitrates are all bound as bidentate ligands. The unit cell for Ln = Er contains two distinct molecules; one with three bidentate nitrates and one with two bidentate and one monodentate nitrate. The Tm and Yb complexes have one molecule in the unit cell with two bidentate and one monodentate nitrate ligands. The monodentate nitrates are hydrogen bonded to ethanol in the Tm and Yb structures but not in the Er complex. The infrared spectra of the three classes of complex do not readily permit identification of the monodentate nitrate groups. Electrospray mass spectrometry indicates that redistribution/ionisation reactions occur in solution. Ions formed by solvolysis reactions are attributed to gas phase processes associated with the electrospray technique. Tandem mass spectrometry for the La, Ho and Yb complexes shows that in the gas phase loss of Cy3PO is the sole fragmentation pathway for all but the Yb complex where the higher energy required for initial fragmentation leads to a more complex fragmentation pattern. 相似文献
85.
《Electroanalysis》2004,16(21):1785-1790
Binaphthyl‐based crown ethers incorporating anthraquinone, benzoquinone, and 1,4‐dimethoxybezene have been synthesized and tested for Rb+ selective ionophores in the poly(vinyl chloride) (PVC) membrane. The membrane containing NPOE gave a better Rb+ selectivity than those containing either DOA or BPPA as a plasticizer. The response was linear within the concentration range of 1.0×10?5–1.0×10?1 M and the slope was 54.7±0.5 mV/dec. The detection limit was determined to be 9.0×10?6 M and the optimum pH range of the membrane was 6.0–9.0. The ISE membrane exhibits good selectivity for Rb+ over ammonium, alkali metal, and alkaline earth metal ions. Selectivity coefficients for the other metal ions, log KPot were ?2.5 for Li+, ?2.4 for Na+, ?2.0 for H+, ?1.0 for K+, ?1.2 for Cs+, ?1.6 for NH4+, ?4.5 for Mg2+, ?5.0 for Ca2+,?4.9 for Ba2+. The lifetime of the membrane was about one month. 相似文献
86.
Wenzel TJ Freeman BE Sek DC Zopf JJ Nakamura T Yongzhu J Hirose K Tobe Y 《Analytical and bioanalytical chemistry》2004,378(6):1536-1547
Chiral crown ethers 1 and 5 are useful enantiomeric discriminating agents in 1H NMR spectroscopy for neutral and protonated primary amines, amino acids, and amino alcohols. The presence of the carboxylic acid groups in 1 and 5 provide sites at which ytterbium(III) can bind. Adding ytterbium(III) nitrate to crown–substrate mixtures in methanol-d4 causes shifts in the spectra of substrates and often enhances the chiral discrimination in the 1H NMR spectrum. The enhancement in enantiomeric discrimination that occurs in the presence of ytterbium(III) allows lower concentrations of the crown ether to be used in chiral recognition studies. Several amide derivatives of 1 were prepared and evaluated as chiral NMR discriminating agents, although except for 1e, these were less effective than 1. 相似文献
87.
Phosphoraneiminato Complexes of Iodine. Syntheses and Crystal Structures of Ph3PNIO2 and Ph3PNSiMe3 · I2 Ph3PNIO2 has been prepared as yellow crystals by the reaction of Ph3PNSiMe3 with I2O5 in boiling acetonitrile, whereas the molecular complex Ph3PNSiMe3 · I2 is formed as brown crystals by the reaction of Ph3PNSiMe3 with iodine in acetonitrile solution. Both complexes were characterized by crystal structure determinations. Ph3PNIO2: Space group P21/n, Z = 4, 2 858 observed unique reflections, R = 0.039. Lattice dimensions at 19°C: a = 972.8(2), b = 1 743.4(3), c = 1 073.7(2) pm, β = 115.46(3)°. The compound forms monomeric molecules with pyramidal geometry at the iodine atom. The bond angle PNI (126.9°) is unusually small; the PN bond length of 159.2 pm corresponds with a double bond. Ph3PNSiMe3 · I2: Space group P1 , Z = 2, 3 560 observed unique reflections, R = 0.033. Lattice dimensions at 19°C: a = 941.2(2), b = 1 041.7(2), c = 1 287.4(3) pm, α = 78.34(1)°, β = 72.00(2)°, γ = 86.08(2)°. The compound forms monomeric molecules, in which the I2 molecule and the nitrogen atom of the phosphoraneimine molecule realize a linear N? I? I axis with a bond length N? I of 243.2 pm. 相似文献
88.
Chuqiao Tu Kazimierz Surowiec Richard A. Bartsch 《Journal of inclusion phenomena and macrocyclic chemistry》2007,58(3-4):361-366
A di-ionizable p-tert-butylcalix[4]arene-1,3-thiacrown-5 ether extractant was synthesized. Its cone conformation and polyether ring attachment
regioselectivity were verified by NMR spectroscopy. The metal ion-complexing properties of this ligand were evaluated by solvent
extractions of metal cations from aqueous solutions into chloroform. The ligand was found to be an efficient extractant with
Ba2+ selectivity in competitive solvent extraction of alkaline earth metal cations. It also exhibits high extraction ability for
Pb2+ and for Hg2+ in single species solvent extractions. 相似文献
89.
Summary The elution behavior of alkali and earth alkaline cations has been studied on a newly synthesized weak cationexchanger (WCX). Applying this stationary phase isocratic separation of these cations is possible. The dependence of retention on competing ion concentration is described via a simple model. The influence of crown ethers as well as organic eluent additives on selectivity and peak efficiency is demonstrated. With optimized separation such cations can be determined with detection limits of about 0.5 ppm using a conductivity detector without ion suppression. 相似文献
90.
Ewa Lada Xiubin Lei Marek K. Kalinowski 《Monatshefte für Chemie / Chemical Monthly》1992,123(5):425-433
Summary The formation constants,K
S, of the 18-crown-6 complex with thallium(I) ion were studied by polarographic measurements in binary mixtures of acetonitrile, acetone, tetrahydrofuran, and dimethylsulfoxide with water, as a function of the solvent mole fraction. In all the cases, the variation of the stability constant can be described by the empirical relation logK
S=a[(–1)/(2+1)]+b where stands for relative permittivity of a given mixture anda andb mark the regression coefficients. The values ofa calculated for four series of binary mixtures showed correlation with the Gutmann donor numbers of the neat organic solvents which form the mixture.On leave from the Department of Chemistry, Jingzhou Teacher's College, Jingzhou, Hubei, China 相似文献