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71.
Maverick AW Laxman RK Hawkins MA Martone DP Fronczek FR 《Dalton transactions (Cambridge, England : 2003)》2005,(1):200-206
The tetradentate Schiff-base ligand SIXH2 (alpha,alpha-bis(salicylimino)-m-xylene), prepared from salicylaldehyde and m-xylylenediamine, forms cofacial binuclear complexes with Pd and Cu. Of the two isomers possible (trans-syn and trans-anti) for M2(SIX)2, these complexes crystallize exclusively as the trans-anti isomer. In ansolvous Pd2(SIX)2, the metal-containing planes are approximately parallel, with PdPd 4.416(1) A. Pd2(SIX)2 also forms a crystalline solvate, in which the molecules adopt a more open conformation with longer metal-metal distances (5.109(1) and 5.112(1) A). The M...M distance is significantly longer in Cu2(SIX)2 (6.653(1) A), because of conformational changes in the m-xylylene moieties and substantial tetrahedral distortion about Cu. 相似文献
72.
Summary Thorium and zirconium can be quantitatively precipitated by quinaldinic acid atph 2.7 and 3, respectively. As the precipitates are of nonstoichiometric composition they are to be ignited to oxides. By this reagent thorium can be quantitatively separated from arsenic (As3+), mercury (Hg2+), rare earths, manganese, magnesium and alkaline earths and zirconium from all the aforesaid ions excepting rare earths which contaminate to a slight extent. 相似文献
73.
A method was developed for direct determination of minor and trace amounts of Cr, Mn, Cu, Ni, Co, Li, Pb, Cd, Bi, Sb, Be and Ag in silicate rock, lake and stream sediments using a microwave oven dissolution method and a multi-element graphite furnace atomic absorption spectrometer equipped with a Zeeman-effect background correction device. The measurement technique was also suitable for direct determination of trace and ultra-trace amounts of these elements in drinking and seawater samples. A rock or sediment sample was brought into solution in a Teflon vessel by heating in a microwave oven with a mixture of hydrofluoric acid and aqua regia, followed by a further heating with a mixture of boric acid and ethylenediaminetetraacetic acid. The specified elements were directly determined in a group of four elements in one firing and eight elements in two firings from this solution or from a diluted solution using the optimum operating parameters developed in this work. The method, tested with 23 international reference rocks and sediments and seven international quality control and reference water samples, showed good to excellent agreement with the recommended values. 相似文献
74.
Summary Fifteen palladium(II) square-planar complexes containing monodentate and/or bidentate anti- and syn-furan-2-aldoxime (FDH) have been isolated and characterized by elemental analysis, molecular weight determination, conductance studies, magnetic moments and i.r. spectral studies. The monodentate ligand coordinates through the nitrogen atom while the bidentate ligand coordinates through the furan oxygen atom and the nitrogen atom. The C-O-C stretching frequency of the furan ring may be taken as the criterion for the denticity of this ligand and is observed at 1240 and 1270 cm– in anti- and syn-furan-2-aldoxime respectively. A shift to lower frequency occurs (in the complex) if the ligand is bidentate, however this frequency is unaffected if the ligand is monodentate. 相似文献
75.
A simple and sensitive method for the determination of isoproturon, a widely used herbicide is described here which is based on alkaline hydrolysis of isoproturon to its corresponding primary amine followed by diazotization and coupling with p-aminoacetophenone in alkaline medium. The absorption maxima of the coloured compound formed is measured at 525 nm. Beer's law is obeyed over the concentration range of 0.5-5.0 mug in a final solution volume of 25 ml (0.02-0.2 ppm). The molar absorptivity and Sandell's sensitivity were found to be 8.6x10(5) l mol(-1) cm(-1) and 0.0002 mug cm(-2), respectively. The method has been satisfactorily applied to the determination of isoproturon in environmental and biological samples. 相似文献
76.
Tara Chandra Gupta Abani K. Bhattacharya 《Fresenius' Journal of Analytical Chemistry》1960,172(6):428-430
Summary The only method recommended for the direct estimation of ferric iron in presence of HCl is to reduce the ferric iron to ferrous iron and then to titrate against KMnO4 solution by adding Reinhardt-Zimmermann reagent (MnSO4 + H2SO4 + H3PO4). The solubility of the phosphato complexes of ferric chloride and phosphoric acid is much reduced by adding a nonaqueous solvent, ethyl alcohol or acetone. This property has been availed of to find out a method of estimating ferric iron directly against standard solution of phosphoric acid in aqueous-nonaqueous medium using K4Fe(CN)6 or cupferron as external indicators. A slight discrepancy at the end point, however, exists in the direct titration but it can be removed by applying a correction factor determined from the estimated results. 相似文献
77.
Computations of the Diels-Alder (DA) reactions of azaphosphole representative namely, thiazolo[3,2-d][1,4,2]diazaphosphole with 1,3-butadiene and isoprene at the density functional theory level reveal concerted mechanisms via asynchronous transition states. The activation energies (B3LYP/6-311++G**// B3LYP/6-311G**), 16-19 kcal mol−1, are much smaller than the value (32.57 kcal mol−1) calculated for the DA reaction of the non-phosphorus analogue, imidazo[2,1-b]thiazole with 1,3-butadiene. An electron-withdrawing group at the 3-position of the dienophile enhances both stereo- and regioselectivities, which agree nicely with the experimental values. Inclusion of solvent effect (PCM model) reveals that the stereo- and regioselectivities are not affected appreciably. The relative stabilities of the transition structures corresponding to the endo/exo stereoisomers and meta (P/Me, 1:3)/para (P/Me, 1:4) regioisomers have been rationalized on the basis of the secondary molecular orbital interactions. 相似文献
78.
Study of EPR, optical properties and electrical conductivity of vanadyl doped Bi2O3.PbO.B2O3 glasses
Gahlot PS Agarwal A Seth VP Sanghi S Gupta SK Arora M 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(6):1189-1194
Heavy metal based oxide glasses having composition xBi(2)O(3).(0.30 - x)PbO.0.70B(2)O(3) have been prepared (0.00 < or = x < or = 0.15, mol%) containing 2.0mol% of V(2)O(5) by normal melt-quenching technique. Electron paramagnetic resonance (EPR), optical spectra and dc conductivity of these glasses have been studied. Spin Hamiltonian parameters (SHP) of VO(2+) ions, dipolar hyperfine parameter, P and Fermi contact interaction parameter, K, molecular orbital coefficients (alpha(2) and gamma(2)) and optical band gap have been calculated. It is observed that in these glasses, the tetragonal nature of V(4+)O(6) complex increases with Bi(2)O(3) content. Increase in Bi(2)O(3):PbO ratio results in the contraction of 3d(xy) orbit of the unpaired electron in the vanadium ion, and the SHP are dependent on the theoretical optical basicity, Lambda(th). In present glasses, the conductivity (activation energy) first decreases (increases) with increase in mol% of Bi(2)O(3) content upto x = 0.08 and then shows a maxima (minima) at x = 0.10 and then starts decreasing (increasing) upto x < or = 0.15 with mol% of Bi(2)O(3) content. 相似文献
79.
Mareque-Rivas JC Prabaharan R Parsons S 《Dalton transactions (Cambridge, England : 2003)》2004,(10):1648-1655
Ligands derived from the tripodal N4 ligand tris(pyridylmethyl)amine ((pyCH2)3N, tpa) of general formula (6-RNHpyCH2)nN(CH2py)(3-n)(R = H, n= 1-3 L(1-3); R = neopentyl, n= 1-3 L'(1-3)) were used to elucidate and quantify the magnitude of the effects exerted by hydrogen bonding and hydrophobic environments in the zinc-water acidity of their complexes. The pKa of the zinc-bound water molecule of [(L(1-3))Zn(OH2)]2+ and [(L'(1-3))Zn(OH2)]2+ 1'-3' was determined by potentiometric pH titrations in water (1-3) or water-ethanol (1:1) (1'-3'). The zinc(II) water acidity gradually increases as the number of -NH2 hydrogen bonding groups adjacent to the water molecule increases. Thus, the zinc-bound water of [(L3)Zn(OH2)]2+ and [(tpa)Zn(OH2)]2+ deprotonate with pKa values of 6.0 and 8.0, respectively. The pKa of the water molecule, however, is only raised from 8.0 in [(tpa)Zn(OH2)]2+ to 9.1 in [(bpg)Zn(OH2)]+ (bpa =(pyCH2)2N(CH2COO-)). Moreover, the acidity of the zinc-bound water of several of the five-coordinate zinc(II) complexes with the hydrogen bonding groups is greater than that of four-coordinate [((12)aneN3)Zn(OH2)]2+ (pKa = 7.0). This result shows that the magnitude of the effect exerted by the hydrogen bonding groups can be larger than that induced by changing one neutral by one anionic ligand, and/or even by changing the coordination number of the zinc(II) centre. The X-ray structure of [(L'2)Zn(OH)]ClO4 2' and [(L'3)Zn(OH)]ClO4.CH3CN 3'.CH3CN is reported, and show the neopentylamino groups forming N-H...O hydrogen bonds with the zinc-bound hydroxide. Although, which have hydrogen bonding and hydrophobic groups, have a zinc-bound water more acidic than [(tpa)Zn(OH2)]2+, their pKa is not always lower than that of 1-3. This result suggests that a hydrogen bonding microenvironment may be more effective than a hydrophobic one to increase the zinc-water acidity. 相似文献
80.