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61.
Two new coordination polymers of PbII complexes with bridging 4,4′‐[(1E)‐ethane‐1,2‐diyl]bis[pyridine] (ebp), thiocyanato, and acetato ligands, [Pb(μ‐SCN)2(μ‐ebp)1.5]n ( 1 ) and {[Pb(μ‐OAc)(μ‐ebp)](ClO4)}n ( 2 ), were synthesized and characterized by elemental analysis, FT‐IR, 1H‐ and 13C‐NMR, thermal analysis, and single‐crystal X‐ray diffraction. In 1 , the Pb2+ ions are doubly bridged by both the ebp and the SCN− ligands into a two‐dimensional polymeric network. The seven‐coordinate geometry around the Pb2+ ion in 1 is a distorted monocapped trigonal prism, in which the Pb2+ ions have a less‐common holodirected geometry. In 2 , the Pb2+ ions are bridged by AcO− ligands forming linear chains, which are also further bridged by the neutral ebp ligands into a two‐dimensional polymeric framework. The Pb2+ ions have a five‐coordinate geometry with two N‐atoms from two ebp ligands and three O‐atoms of AcO−. Although ClO acts as a counter‐ion, it also makes weak interactions with the Pb2+ center. The arrangement of the ligands in 2 exhibits hemidirected geometry, and the coordination gap around the Pb2+ ion is possibly occupied by a configurationally active lone pair of electrons. 相似文献
62.
Summary Mono, bis and tris complexes of rhodium(III) with phenyl-2-picolylketone-2-pyridyl hydrazone (PPKPyH) have been characterized. In every case, the imino-proton of PPKPyH shows marked acidity associated with the coordination to rhodium(III). Electronic spectra show that all complexes are octahedral. The B-values suggest a strong covalency in the metal-ligand -bond and the Dq-values indicate a medium-strong ligand field. The magnetic susceptibility indicates that PPKPyH forms low-spin complexes with rhodium(III).1H n.m.r. spectra show that the tris(ligand) complexes arecis isomers. I.r. spectra show that the ligand is neutral or monobasic tridentate or bidentate. Far i.r. studies show that [Rh(PPKPyH)X3] · 2 H2O (X = Cl, Br or I) aremer isomers. The effect of pH variation on the rection products is also discussed. 相似文献
63.
A sensitive cathodic stripping voltammetric method is developed for determination of lead(II), with adsorptive collection of complexes with Pyrogallol red (PGR) on to a hanging mercury drop electrode. After accumulation of the complex at −0.80 V vs. Ag/AgCl reference electrode, the potential is scanned in a negative direction from −0.20 to −0.50 V with differential pulse method. Then the reduction peak current for the lead(II)-PGR complex is measured at −0.39 V. The influence of reagent and instrumental variables was completely studied by factorial design analysis. The optimum analytical conditions for the determination of lead(II) were established. Under optimum conditions, lead(II) determined in the range of 0.1-30.0 ng ml−1 with a limit of detection of 0.06 ng ml−1. The method is successfully applied to determination of lead(II) in water sample. 相似文献
64.
Mir Ali Farajzadeh Mortaza Ebrahimi Ali Ranji Elham Feyz Vali Bejani Amir Abbas Matin 《Mikrochimica acta》2006,153(1-2):73-78
High performance liquid chromatography (HPLC) and gas chromatography (GC) are introduced for analysis of polymer lubricants
(stearamide, oleamide and erucamide). In the HPLC method, a reverse phase octadecylsilane (ODS) column along with acetonitrile/methanol
(60:40) as a mobile phase were used. Detection of analytes was performed by a UV detector at 202 nm. The analysis time was
less than 8 min. In the GC method, polar capillary column and flame ionization detector (FID) were used for separations and
detection, respectively. The analysis time by GC was longer than HPLC and was about 30 min. Limits of detection, linear range
and repeatability of both methods are similar, but determination of oleamide in real samples by HPLC method is difficult due
to complexity of the initial part of HPLC chromatogram in polyethylene samples. That problem is not observed in the GC method.
Detection limits in both methods for all analytes are lower than 0.003% which are much lower than the amount of lubricants
in commercial polymers (0.05–0.2%). 相似文献
65.
Summary
Bis(cyclopentadienyl)titanium(IV) diisothiocyanate [(Cp)2-Ti(NCS)2] reacts with MCl2 (M = Cu, Pd or Pt), [CuCl(PPh3)3], [RuCl2(PPh3)3] and [RuCl2(DMSO)4] (DMSO = dimethylsulphoxide) giving solid compounds of stochiometry [(Cp)2Ti(-NCS)2MCl2] (M = Cu, Pd or Pt), [(Cp)2Ti(-NCS)2CuCl(PPh3)], [(Cp)2Ti(-NCS)2-RuCl(PPh3)2]Cl and [(Cp)2Ti(-NCS)2RuCl2(DMSO)2]. These products have been characterized by physicochemical and spectroscopic methods. 相似文献
66.
67.
68.
We use the stochastic rotation dynamics algorithm to investigate the packaging of flexible and semiflexible polymers into a capsid that is permeable to solvent molecules. The model takes into account hydrodynamic interactions arising due to local flow. The flexible chain maintains a random configuration as it is being fed into the capsid, in contrast to the semiflexible chain, whose configuration is initially spool-like, becoming more random at high packing. We measure the packing rate, which is found to decrease with the percentage of the chain packed and highlight the difference between the flexible and semiflexible chains. Reflecting experiments, we find pauses in the packing process for individual chains as the motor loses grip of the fluctuating beads. We also find that hydrodynamics is important, in that the packaging rate is faster when flow is included. 相似文献
69.
Garner DK Fitch SB McAlexander LH Bezold LM Arif AM Berreau LM 《Journal of the American Chemical Society》2002,124(34):9970-9971
The synthesis and properties of mononuclear zinc methoxide ([(ebnpa)Zn-OCH3]ClO4) (1) and hydroxide ([(ebnpa)Zn-OH]ClO4) (2) complexes of a new mixed nitrogen/sulfur ligand (ebnpa = N-2-(ethylthio)ethyl-N,N-bis(6-neopentylamino-2-pyridylmethyl)amine) are reported. The structures of 1 and 2 were determined by X-ray diffraction. Each possesses a single zinc-coordinated anion (methoxide or hydroxide) and exhibits an overall trigonal bipyramidal geometry. Structural and spectroscopic studies indicate the presence of two hydrogen-bonding interactions involving the oxygen atom of the zinc-bound anion in each complex. Treatment of [(ebnpa)Zn-OH]ClO4 with CH3OH results in the formation of an equilibrium mixture of 1 and 2. 1H NMR spectroscopic methods were used to examine the equilibrium as a function of temperature, yielding KMe (304 K) = 0.30(8), DeltaHMe = -0.9(1) kcal/mol, and DeltaSMe = -5(1) eu. The negative enthalpy indicates that spontaneous zinc alkoxide formation from a hydroxide precursor occurs in this system at low temperature. Using the experimentally determined DeltaHMe value, we found the homolytic Zn-O bond dissociation energy (BDE) in the Zn-OCH3 unit to be approximately -14 kcal/mol relative to the Zn-O BDE in the Zn-OH unit. 相似文献
70.
X-Ray Structural Analyses of Cyclododecasulfur (S12) and Cyclododecasulfur-1-Carbon-disulfide (S12 · CS2) S12 · CS2 crystallizes in space group R&3macr;m–D with hexagonal lattice constants a = 1066.8(3), c = 1155.1(4) pm, Z = 3, dcalc. = 2.04 g · cm?3. The S12 molecules occupy sites of D3d symmetry with bond distance (dss) of 205.4(1) pm, bond angles (α) of 105.80(5) and 106.65(6)º and torsional angle (τ) of 87.20(7)º. The CS2 molecule interacts only very weakly with the S12 units. S12 crystallizes in space group Pnnm–D with lattice constants a = 472.5(2), b = 910.4(3), c = 1453.2(3) pm, Z = 2, dcalc = 2.045 g · cm?3. The molecules with mean parameters d = 205.2 pm, α 106.6º, τ 88.0º occupy sites of C2h symmetry. 相似文献