混合三烃基锡衍生物的研究：X.甲基二环己基锡二硫代磷酸酯的合成及生…

合成了１０种甲基二环己基锡－Ｏ，Ｏ－二烃基二硫代磷酸酯，利用ＩＲ，ＮＭＲ，ＭＳ及元素分析确证了化合物的结构，生物活性测试结果表明，这类化合物具有较高的杀螨和除草活性。     

Substituted Diorganotin(IV) O,O’-Alkylene Dithiophosphates: Synthesis and Spectral Aspects

Six new substituted diphenyltin(IV) O,O′-alkylene dithiophosphates, (C₆H₅)₂Sn(X)S(S) POGO [G = —CH₂C(CH₃)₂CH₂—, X = Cl (1), SCN (3), ClO₄ (5); G = —CH₂C (C₄H₉)(C₂H₅)CH₂—, X = Cl (2), SCN (4), ClO₄ (6)], were synthesized by the reaction of the corresponding ammonium salts of the O,O’-alkylene dithiophosphates with an appropriate organotin(IV) chloride. The compounds were characterized on the basis of elemental and spectral analyses (ESI mass spectrometry, IR, ¹H, ¹³C, ³¹P, and ¹¹⁹Sn NMR). The presence of a four-coordinated Sn atom and monodentate O,O’-alkylene dithiophosphate moiety in compounds 1–4 as well as bidentate O,O’-alkylene dithiophosphate unit in compounds 5,6 is established.     

Synthesis, Characterization and Crystal Structure of [Ni（S2P{O}OC6H4CH3-p）（dppv）]

O-（p-tolyl）dithiophosphato nickel complex [Ni（S2P{O}OC6HaCH3-p）（dppv）] has been synthesized by the treatment of （dppv）NiCl2 （dppv = Ph2PCH=CHPPh2） with （p-CH3C6HaO）2P{S}SH＇Et2NH in THF. The new complex was fully characterized by elemental analysis, IR, 1H NMR, 31p NMR spectroscopies and thermo-gravimetric analysis. The molecular structure of the complex was established by X-ray crystallography. The crystal crystallizes in monoclinic, space group P21/c with a = 9.2739（5）, b = 17.8803（8）, c = 20.1879（12） A, fl = 93.269（5）, V = 3342.1（3） A3, Z = 4, C33H29NiO2P3S2, Mr = 673.30, Dc = 1.338 g/cm3, F（000） = 1392 and #（MoKa） = 0.877 rnm-l. The final R = 0.0578 and wR = 0.1045 for 4138 observed reflections with 1 〉 20（/） and R = 0.1050 and wR = 0.1204 for all data. The Ni centre atom adopts a NiP2S2 square-planar geometry with two phosphorus atoms from the dppv ligand and two sulfur atoms from the O-（p-tolyl）dithiophosphate ligand. The most interesting structural feature of the title complex resides in its 1D helical chain structure constructing via intermolecular C-H＇＂O secondary interactions along the b-axis. The adjacent helical chains running in opposite directions are connected into a 1D double-stranded helical chain and further linked into a 2D supramolecular network by weak C-H.--C interaction.     

Sodium dithiophosphate(V): Crystal structure, sodium ionic conductivity and dismutation

Na₃PO₂S₂ was synthesized from the corresponding undecahydrate by freeze–drying. It dismutates at temperatures above 350 °C into Na₃PO₃S and Na₃POS₃. The crystal structure of Na₃PO₂S₂ was determined from X-ray powder diffraction data, and refined using the Rietveld technique (Pbca, a=17.5359(2) Å, b=11.3044(1) Å, c=5.8656(1) Å, R_F²=8.45%, R_p=4.80%, R_wp=6.79%). The baricenters of the PO₂S₂-tetrahedra are arranged in the sense of a hexagonal close packing. One of the P---O bonds of these tetrahedra is oriented parallel to the crystallographic c-axis with the POS₂-groups in an eclipsed mutual orientation. The crystal structure of Na₃PO₂S₂ displays a close relationship to the ones of Ca₃CrN₃ and Na₃POS₃. Above 330 °C, Na₃PO₂S₂ can be regarded as a fast ionic conductor (with σ>10⁻⁵ S cm⁻¹).     

Crystal and molecular structures of the Rh[(C2H5O)2PS2]3 and Co[(C6H5O)2PS2]3 chelate compounds

The crystal structures of the Rh[(EtO)₂PS₂]₃ (I) and Co[(PhO)₂PS₂]₃ (II) chelate compounds were determined from X-ray diffraction (XRD) data (CAD-4 diffractometer, MoK _β radiation, 1193 F _hkl , R = 0.0516 for I and 513 F _hkl , R = 0.0305 for II). Crystals I are monoclinic: a = 14.233(3) Å, b = 13.570(3) Å, c = 14.272(3) Å; β = 90.66(3)°, V = 2756.3(10) ų, Z = 4, ρ_calc = 1.587 g/cm³, space group C2/c. Crystals II are trigonal: a = 15.149(2) Å, c = 30.306(6) Å; V = 6023.2(16) ų, Z = 6, ρ_calc = 1.493 g/cm³, space group R3ˉ. Structures I and II consist of discrete mononuclear molecules. The coordination polyhedra of the M atoms (M = Rh, Co) are distorted octahedra formed by six sulfur atoms of three cyclic bidentate (RO)₂ PS₂⁻ ligands. Original Russian Text Copyright ? 2008 by R. F. Klevtsova, L. A. Glinskaya, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 2, pp. 330–334, March–April, 2008.     

Extraction of arsenic as the diethyl dithiophosphate complex with supercritical fluid and quantitation by cathodic stripping voltammetry

The separation of arsenic based on in situ chelation with ammonium diethyl dithiophosphate (ADDTP) has been carried out using methanol-modified supercritical CO₂. Aliquots of extract were added to an electroanalytical cell and arsenic was determined by square wave cathodic stripping voltammetry (SWCSV) at a hanging mercury drop electrode (HMDE). Quantitative extractions of As(DDTP)₃ were achieved when the experiments were carried out at a pressure of 2500 psi, a temperature of 90 °C, 2.0 mL of methanol, 20.0 min of static extraction and 5.0 min of dynamic extraction in the presence of 18 mg of ADDTP. Analysis of arsenic was made using 150 mg L⁻¹ of Cu(II) in 1 M HCl solution as supporting electrolyte in the presence of ADDTP as ligand. Preconcentration was carried out by deposition at a potential of −0.50 V and the intermetallic compound Cu_xAs_y was reduced at a potential of −0.77 to −0.82 V, depending on ligand concentration. The results showed that the presence of ligand plays an important role, increasing the method's sensitivity and preventing the oxidation of As(III). The calibration graph of the As(DDTP)₃ solution was linear from 0.8 to 12.5 μg L⁻¹ of arsenic (LOD 0.5 μg L⁻¹, R = 0.9992, t_acc = 60 s). The method was validated using carrot pulp spiked with arsenic solution. This method was applied to the determination of arsenic in samples of carrots, beets and irrigation water. Arsenic in beets was: skin 4.10 ± 0.18 mg kg⁻¹; pulp 3.83 ± 0.19 mg kg⁻¹ and juice 0.71 ± 0.09 mg L⁻¹; arsenic in carrots was: skin 2.15 ± 0.09 mg kg⁻¹; pulp 0.59 ± 0.11 mg kg⁻¹ and juice 0.71 ± 0.03 mg L⁻¹. Arsenic in water were: Chiu-Chiu 0.08 mg L⁻¹, Inacaliri 1.12 mg L⁻¹, and Salado river 0.17 ± 0.07 mg L⁻¹.     

Determination of mercury in biological samples by cold vapor atomic absorption spectrometry following cloud point extraction with salt-induced phase separation

Method development for the pre-concentration of mercury in human hair, dogfish liver and dogfish muscle samples using cloud-point extraction and cold vapor atomic absorption spectrometry is demonstrated. Before the extraction, the samples were submitted to microwave-assisted digestion in a mixture of H₂O₂ and HNO₃. Cloud point extraction was carried out using 0.5% (m/v) ammonium O,O-diethyldithiophosphate (DDTP) as the chelating agent and 0.3% (m/v) Triton X-114 as the non-ionic surfactant. Phase separation was induced after the addition of Na₂SO₄ to a final concentration of 0.2 mol L⁻¹. Aliquots of the final extract were transferred to PTFE tubes and NaBH₄ and HCl were added. The mercury vapor was driven to a non-heated quartz tube for measuring the absorbance. The results obtained with salt-induced phase separation were in good agreement with the certified values at a 95% confidence level. An enrichment factor of 10 allowed a detection limit of 0.4 ng g⁻¹ to be obtained, which demonstrates the high sensitivity of the proposed procedure for the determination of mercury at trace levels.     

Synthetic,spectral as well as in vitro antimicrobial studies on some bismuth(III) bis(N,N‐dialkyldithiocarbamato) alkylenedithiophosphates

Mixed sulfur donor ligand complexes of the type bismuth(III) bis(N,N‐dialkyldithiocarbamato) alkylenedithiophosphate, [R₂NCS₂]₂BiS₂POGO [where R = CH₃ and C₂H₅; G = ‐CH₂‐C(C₂H₅)₂‐CH₂‐, ‐CH₂‐C(CH₃)₂‐CH₂‐, ‐CH(CH₃)‐CH(CH₃)‐ and ‐C(CH₃)₂‐C(CH₃)₂‐] were synthesized in 1:1 molar ratio of bismuth(III) bis(N,N‐dialkyldithiocarbamate) chloride and ammonium alkylenedithiophosphate in refluxing benzene and characterized by melting point, molecular weight determinations, elemental analysis (C, H, N, Bi and S) and spectral [UV, IR,NMR (¹H,¹³C and ³¹P) and powder X ray diffraction] studies; all these studies were in good agreement with the synthesized complexes. These newly synthesized derivatives are yellow and brown colored solids and are soluble in common organic solvents like benzene, chloroform, dichloromethane and DMF. Based on the physicochemical and spectral studies, a tentative structure of these newly synthesized complexes was assigned and the average particle size of the synthesized complexes determined by powder XRD, showing that nano range polycrystalline particles were formed with a monoclinic crystal system. These complexes were also screened for their antimicrobial activities using the well diffusion method. The free ligands as well as their mixed metal complexes were tested in vitro against four bacterial strains: two Gram‐positive, Staphylococcus aureus (ATCC 9144) (G⁺) and Bacillus subtilis (ATCC 6051), (G⁺) and two Gram‐negative, Escherichia coli (ATCC 9637) (G^?) and Pseudomonas aeruginosa (ATCC 25619) (G^?) to assess their antimicrobial properties. The results were indeed positive and exhibited good antibacterial effects. Chloroamphenicol used as a standard for comparison and synthesized complexes showed good antibacterial effects over chloroamphenicol. On the basis of these studies, the synthesized complexes help to understand the different structural and biological properties of main group elements with sulfur donor ligands. Copyright © 2010 John Wiley & Sons, Ltd.     

Simple hollow fiber renewal liquid membrane extraction method for pre-concentration of Cd(II) in environmental samples and detection by Flame Atomic Absorption Spectrometry

A hollow fiber renewal liquid membrane (HFRLM) extraction method to determine cadmium (II) in water samples using Flame Atomic Absorption Spectrometry (FAAS) was developed. Ammonium O,O-diethyl dithiophosphate (DDTP) was used to complex cadmium (II) in an acid medium to obtain a neutral hydrophobic complex (ML₂). The organic solvent introduced to the sample extracts this complex from the aqueous solution and carries it over the poly(dimethylsiloxane) (PDMS) membrane, that had their walls previously filled with the same organic solvent. The organic solvent is solubilized inside the PDMS membrane, leading to a homogeneous phase. The complex strips the lumen of the membrane where, at higher pH, the complex Cd-DDTP is broken down and cadmium (II) is released into the stripping phase. EDTA was used to complex the cadmium (II), helping to trap the analyte in the stripping phase. A multivariate procedure was used to optimize the studied variables. The optimized variables were: sample (donor phase) pH 3.25, DDTP concentration 0.05% (m/v), stripping (acceptor phase) pH 8.75, EDTA concentration 1.5 × 10⁻² mol L⁻¹, extraction temperature 40 °C, extraction time 40 min, a solvent mixture N-butyl acetate and hexane (60/40%, v/v) with a volume of 100 μL, and addition of ammonium sulfate to saturate the sample. The sample volume used was 20 mL and the stripping volume was 165 μL. The analyte enrichment factor was 120, limit of detection (LOD) 1.3 μg L⁻¹, relative standard deviation (RSD) 5.5% and the working linear range 2-30 μg L⁻¹.