蒙脱土表面键合配位体固相萃取填料的制备及其对重金属离子的吸附性能

通过酸洗、硅烷偶联剂表面活化、键合苯甲酰异硫氰酸酯对蒙脱土进行改性,制得新型固相萃取(SPE)材料。 采用红外光谱、扫描电子显微镜、X射线光电子能谱表征了改性蒙脱土的结构和形貌。 考察了制备的SPE填料对水中As³⁺、Bi³⁺、Cu²⁺、Sb³⁺、Sn²⁺和Pb²⁺的吸附性能,确定了最佳固相萃取条件,对6种金属离子吸附容量分别为10.83、11.92、12.67、10.43、10.01及10.54 mg/g。 通过SPE与电感耦合等离子体质谱联用测定了样品中As³⁺、Bi³⁺、Cu²⁺、Sb³⁺、Sn²⁺和Pb²⁺ 6种重金属离子的含量,检出限分别为0.024、0.013、0.075、0.037、0.011和0.064 μg/L。     

Synthesis, crystal structure and magnetic behavior of two cobalt coordination polymers with 1,2-bis(1,2,4-triazol-1-yl)ethane and dicyanamide

Two cobalt(II) coordination polymers formed from bte (bte = 1,2-bis(1,2,4-triazol-1-yl)ethane), namely [Co(bte)₂(dca)₂]_n (1) and {[Co(bte)(dca)₂] · H₂O}_n (2), have been synthesized and characterized by elementary analyses, IR, thermogravimetric analyses, X-ray diffraction analyses and magnetic measurements. Compound 1 is a double-chain with Co(II) centers bridged by bte, containing metallocycles of [Co₂(bte)₂] and trans dca as termination ligands. In 2, each Co(II) center is bonded by two bridging bte ligands and four dca as μ-1,5-dca in different orientations in the 3D network.     

^1^5N标记邻位芳香羟肟配位体的核磁共振研究

利用稳定同位素的磁性和质量同位素效应已成为研究有机结构化学的重要手段。我们为研究部位芳香及其芝渡金属如Cu(Ⅱ),Ni(Ⅱ),Co(Ⅱ),Fe(Ⅱ)配合物的光     

Studies on the mixed-ligand complexes of copper(II) with gallic acid and pyridine carboxylic acids and their benzologues

Summary The ternary complex formation of copper(II) with gallic acid (gal) and 2-hydroxy nicotinic acid (hyna), 2-mercapto nicotinic acid (mena), salicylic acid (sa) or thiosalicylic acid (tsa) as a second ligand in a 1:1:1 molar ratio has been investigated in 40% (v/v) ethanol using spectrophotometric andpH titration methods. The solution equilibria of the ternary systems have been determined and the stability constants of the mixed complexes has been evaluated. Considering all parameters, the Cu-gal-sa ternary system was proved as a suitable, rapid, and sensitive spectrophotometric indicator for determining traces of copper.The ternary system containingsa obeysBeer's law up to 3.4 µg·ml^–1 copper. The optimum range for the determination of copper (Ringbom) atpH 6.0 ranges from 0.63 to 1.74 µg·ml^–1 of copper. The molar absorptivity of the ternary complex is 1.3×10⁴l·mol^–1·cm^–1.

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Untersuchungen anmixed-ligand — Komplexen von Kupfer(II) mit 3,4,5-Trihydroxybenzoesäure und Pyridincarbonsäuren und ihren C-Homologen

Zusammenfassung Die Bildung ternärer Komplexe von Kupfer(II) mit 3,4,5-Trihydroxybenzoesäure (gal) und 2-Hydroxynicotinsäure (hyna), 2-Mercaptonicotinsäure (mena), Salicylsäure (sa) oder Thiosalicylsäure (tsa) in einem molaren Verhältnis von 1:1:1 wurde mittels spektrophotometrischer und potentiometrischer Methoden in 40% (v/v) Ethanol untersucht. Die Lösungsgleichgewichte der termären Systeme und die Stabilitätskonstanten der gemischten Komplexe wurden bestimmt. Unter Berücksichtigung aller Parameter erwies sich das termäre System Cu-gal-sa als geeigneter schneller und empfindlicher Indikator zur Spurenanalyse von Kupfer.Dassa enthaltende ternäre System gehorcht demBeerschen Gesetz bis zu einer Kupferkonzentration von 3.4 µg·ml^–1. Der optimale Bereich zur Bestimmung von Kupfer (Ringbom) beipH 6.0 erstreckt sich von 0.63 bis 1.74 µg Cu pro ml. Die molare Extinktion des ternären Komplexes beträgt 1.3×10⁴l·mol·cm^–1.

     

手性双膦配体（4S,5S）—（—）—DIOP的合成

不对称催化是由潜手性反应物合成光活性化合物的有效途径,α,β-不饱和氨基酸的氢化立体选择性已达90％以上,L-Dopa的工业化生产则标志着不对称催化氢化开始走向实际应用。高选择性的催化剂一般是一价铑的手性双膦配体络合物,其中DIOP[2,3-O-异丙叉-     

Regioselective cleavage of the bis-benzylidene acetal of d-mannitol under oxidative and reductive conditions: a new approach to C2-symmetric chiral ligands

A highly regioselective oxidative cleavage of 1,3:4,6-di-O-benzylidene-d-mannitol was carried out using NBS and the resultant product was readily converted to the C₂-symmetric chiral ligand, (R,R)-3,4-dihydroxy-1,5-hexadiene. On the other hand, reductive cleavage of 1,3:4,6-di-O-benzylidene-d-mannitol was achieved in a highly regioselective manner using BF₃·OEt₂ and Et₃SiH to give a highly functionalized benzyl ether, which was converted to a synthetically useful C₂-symmetric bis-amino alcohol derivative.     

Syntheses, Crystal Structures and Magnetism of Two New Coordination Polymers [Ni（bix）2Cl2]n and [Co（bix）Cl2]n

The self-assembly reactions of MIICl2 (M = Ni, Co) with the flexible bix ligand [bix = 1,4-bis(imidazole-1-ylmethyl)benzene] yielded a 2D network [NiII(bix)2Cl2]n 1 and a 1D chain [CoII(bix)Cl2]n 2. Their crystal structures have been determined by X-ray single-crystal diffraction analysis. Complex 1 characters a two-dimensional grid-type structure and crystallizes in monoclinic, space group P21/c with a = 7.7231(7), b = 12.7787(9), c = 13.9374(13) , β = 105.419(4)o, C28H28Cl2N8Ni, Mr = 606.19, Ζ = 2, V = 1326.0(2) 3, Dc = 1.518 g/cm3, μ = 0.969 mm-1, F(000) = 628, R = 0.0429 and wR = 0.0783 for 2503 observed reflections (I > 2σ(I)). Compound 2 is a one-dimensional chain and crystallizes in orthorhombic, space group Pbca with a = 11.3696(6), b = 10.2128(6), c = 14.4943(9) , C14H14Cl2CoN4, Mr = 368.12, Z = 4, V = 1683.01(17) 3, Dc = 1.453 g/cm3, μ = 1.334 mm-1, F(000) = 748, R = 0.0317 and wR = 0.0800 for 1778 observed reflections (I > 2σ(I)). Magnetic properties of the title complexes were also investigated.     

Modeling η5‐C5Me4SiMe3 with η3‐C3H5 for DFT study of a tetranuclear yttrium polyhydrido complex [(η5‐C5Me4SiMe3)YH2]4

π‐Allyl (η³‐C₃H₅), a four‐electron donor, was used as a ligand model to replace η⁵‐C₅Me₄SiMe₃ in DFT calculations on the tetranuclear yttrium polyhydrido complex (η⁵‐C₅Me₄SiMe₃)₄Y₄H₈ containing a Y₄H₈ tetrahedral core structure, which may separate the four π‐allyl groups and hence suppress the allyl ligand coupling during the computation. In terms of the calculated core geometry, isomerization energy barrier, charge population, and frontier orbital features of the complex, the η³‐C₃H₅ ligand model is comparable to η⁵‐C₅H₅. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Emission band shape probes of the mixed-valence excited state properties of polypyridyl-bridged bis-ruthenium(II) complexes

The absorption spectra and emission spectral band shapes of several polypyridine-ligand (PP) bridged bis-ruthenium(II) complexes imply that the Ru(II)/Ru(III) electronic coupling is weak in their lowest energy metal to ligand charge transfer (MLCT) excited states. Many of these PP-bridging ligands contain pyrazine moieties and the weak electronic coupling of the excited states contrasts to the strong electronic coupling inferred for the correlated mixed-valence ground states. Although the bimetallic complexes emit at significantly lower energy than their monometallic analogs, the vibronic contributions to their 77 K emission spectra are much stronger than expected based on comparison to the monometallic analogs (around twofold in some complexes) and this feature is characteristic of bimetallic complexes in which the mixed-valence excited states are electronically localized. The weaker excited state than ground state donor/acceptor electronic coupling in this class of complexes is attributed to PP-mediated super-exchange coupling in which the mediating orbital of the bridging ligand (PP-LUMO) is partly occupied in the MLCT excited states, but is unoccupied in the ground states; therefore, the vertical Ru(III)-PP⁻ (MLCT) energy is larger and the mixing coefficient smaller in these excited states than is found for Ru(II)-PP in the corresponding ground states.     

Ethylene and propylene polymerization behavior of a series of bis(phenoxy–imine)titanium complexes

This contribution reports ethylene and propylene polymerization behavior of a series of Ti complexes bearing a pair of phenoxy–imine chelate ligands. The bis(phenoxy–imine)Ti complexes in conjunction with methylalumoxane (MAO) can be active catalysts for the polymerization of ethylene. Unexpectedly, this C₂ symmetric catalyst produces syndiotactic polypropylene. ¹³C NMR spectroscopy has revealed that the syndiotacticity arises from a chain-end control mechanism. Substitutions on the phenoxy–imine ligands have substantial effects on both ethylene and propylene polymerization behavior of the complexes. In particular, the steric bulk of the substituent ortho to the phenoxy–oxygen is fundamental to obtaining high activity and high molecular weight for ethylene polymerization and high syndioselectivity for the chain-end controlled propylene polymerization. The highest ethylene polymerization activity, 3240 kg/mol-cat h, exhibited by a complex having a t-butyl group ortho to the phenoxy–oxygen, represents one of the highest reported to date for Ti-based non-metallocene catalysts. Additionally, the polypropylene produced exhibits a T_m, 140 °C, and syndioselectivity, rrrr 83.7% (achieved by a complex bearing a trimethylsilyl group ortho to the phenoxy–oxygen) that are among the highest for polypropylenes produced via a chain-end control mechanism. Hence, the bis(phenoxy–imine)Ti complexes are rare examples of non-metallocene catalysts that are useful for the polymerization of not only ethylene but also propylene.