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Tolis EJ Teberekidis VI Raptopoulou CP Terzis A Sigalas MP Deligiannakis Y Kabanos TA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(12):2698-2710
Two series of octahedral oxovanadium(IV) compounds, containing charged or neutral axial ligands, with the tetradentate amidate molecules Hcapca and H2capcah of the general formulae trans-[V(IV)OX(capca)]0/+ (where X = Cl- (1.CH2Cl2), SCN- (2), N3 (3), CH3COO- (4), PhCOO- (5), imidazole (6. CH3NO2), and eta-nBuNH2 (7)) and cis-[V(VI)OX(Hcapcah)]0/+ (where X = Cl- (8.0.5CH2Cl2), SCN (9), N3 (10.2CH3OH), and imidazole (11)), were synthesized and characterized by X-ray crystallography (1.CH3OH,8.CHCl3, 9.2CH3CN, 10.CH3CN and cis-[VO(imidazole)(Hcapcah)+) and continuous-wave electron paramagnetic resonance (cw EPR) spectroscopy. In addition to the synthesis, crystallographic and EPR studies, the optical, infrared and magnetic properties (room temperature) of these compounds are reported. Ab initio calculations were also carried out on compound 8 CHCl3 and revealed that this isomer is more stable than the trans isomer, in good agreement with the experimental data. The cw EPR studies of compounds 1-5, that is, the V(IV)O2+ species containing monoanionic axial ligands, revealed a novel phenomenon of the reduction of their A, components by about 10% relative to the N4 reference compounds ([V(IV)O-(imidazole)4]2+ and [V(IV)O(2,2-bipyridine)2]2+). In marked contrast, such a reduction is not observed in compounds 6. CH3NO2-11, which contain neutral axial ligands. Based on the spin-Hamiltonian formalism a theoretical explanation is put forward according to which the observed reduction of Az is due to a reduction of the electron - nuclear dipolar coupling (P). The present findings bear strong relevance to cw EPR studies of oxovanadium(IV) in vanadoproteins, V(IV)O2+-substituted proteins, and in V(IV)O2+ model compounds, since the hyperfine coupling constant, Az, has been extensively used as a benchmark for identification of equatorial-donor-atom sets in oxovanadium(IV) complexes. 相似文献
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Triantafillou GD Tolis EI Terzis A Deligiannakis Y Raptopoulou CP Sigalas MP Kabanos TA 《Inorganic chemistry》2004,43(1):79-91
Reaction of [V(IV)OCl(2)(THF)(2)] in aqueous solution with 2 equiv of AgBF(4) or AgSbF(6) and then with 2 equiv of 2,2'-bipyridine (bipy), 4,4'-di-tert-butyl-2,2'-bipyridine (4,4'-dtbipy), or 4,4'-di-methyl-2,2'-bipyridine (4,4'-dmbipy) affords compounds of the general formula cis-[V(IV)O(OH)(L(NN))(2)]Y [where L(NN) = bipy, Y = BF(4)(-) (1), L(NN) = 4,4'-dtbipy, Y = BF(4)(-) (2.1.2H(2)O), L(NN) = 4,4'-dmbipy, Y = BF(4)(-) (3.2H(2)O), and L(NN) = 4,4'-dtbipy, Y = SbF(6)(-) (4)]. Sequential addition of 1 equiv of Ba(ClO(4))(2) and then of 2 equiv of bipy to an aqueous solution containing 1 equiv of V(IV)OSO(4).5H(2)O yields cis-[V(IV)O(OH)(bipy)(2)]ClO(4) (5). The monomeric compounds 1-5 contain the cis-[V(IV)O(OH)](+) structural unit. Reaction of 1 equiv of V(IV)OSO(4).5H(2)O in water and of 1 equiv of [V(IV)OCl(2)(THF)(2)] in ethanol with 2 equiv of bipy gives the compounds cis-[V(IV)O(OSO(3))(bipy)(2)].CH(3)OH.1.5H(2)O (6.CH(3)OH.1.5H(2)O) and cis-[V(IV)OCl(bipy)(2)]Cl (7), respectively, while reaction of 1 equiv of [V(IV)OCl(2)(THF)(2)] in CH(2)Cl(2) with 2 equiv of 4,4'-dtbipy gives the compound cis-[V(IV)OCl(4,4'-dtbipy)(2)]Cl.0.5CH(2)Cl(2) (8.0.5CH(2)Cl(2)). Compounds cis-[V(IV)O(BF(4))(4,4'-dtbipy)(2)]BF(4) (9), cis-[V(IV)O(BF(4))(4,4'-dmbipy)(2)]BF(4) (10), and cis-[V(IV)O(SbF(6))(4,4'-dtbipy)(2)]SbF(6) (11) were synthesized by sequential addition of 2 equiv of 4,4'-dtbipy or 4,4'-dmbipy and 2 equiv of AgBF(4) or AgSbF(6) to a dichloromethane solution containing 1 equiv of [V(IV)OCl(2)(THF)(2)]. The crystal structures of 2.1.2H(2)O, 6.CH(3)OH.1.5H(2)O, and 8.0.5CH(2)Cl(2) were demonstrated by X-ray diffraction analysis. Crystal data are as follows: Compound 2.1.2H(2)O crystallizes in the orthorhombic space group Pbca with (at 298 K) a = 21.62(1) A, b = 13.33(1) A, c = 27.25(2) A, V = 7851(2) A(3), Z = 8. Compound 6.CH(3)OH.1.5H(2)O crystallizes in the monoclinic space group P2(1)/a with (at 298 K) a = 12.581(4) A, b = 14.204(5) A, c = 14.613(6) A, beta = 114.88(1) degrees, V = 2369(1), Z = 4. Compound 8.0.5CH(2)Cl(2) crystallizes in the orthorhombic space group Pca2(1) with (at 298 K) a = 23.072(2) A, b = 24.176(2) A, c = 13.676(1) A, V = 7628(2) A(3), Z = 8 with two crystallographically independent molecules per asymmetric unit. In addition to the synthesis and crystallographic studies, we report the optical, infrared, magnetic, conductivity, and CW EPR properties of these oxovanadium(IV) compounds as well as theoretical studies on [V(IV)O(bipy)(2)](2+) and [V(IV)OX(bipy)(2)](+/0) species (X = OH(-), SO(4)(2)(-), Cl(-)). 相似文献
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Vaggelis Hondrellis Themistoclis Kabanos Spyros P. Perlepes John M. Tsangaris 《Monatshefte für Chemie / Chemical Monthly》1988,119(10):1091-1101
New complexes of the formulaeM(fur)2·2H2O (M = Mn, Cu, Zn),M(fur)2·3H2O (M = Co, Ni, Cd), Hg2(fur)3Cl2·2H2O, Pd(fur)Cl·H2O and Rh(fur)3·3H2O, wherefurH = 4-chloro-N-(2-furfuryl)-5-sulfamoylanthranilic acid, have been prepared and characterized by conductivity measurements, X-ray powder patterns, thermal methods, effective magnetic moments as well as by IR, ligand field,1H-NMR and ESR spectroscopic studies. The anionfur
– shows a chelated bidentate O(carboxylato), N(imino)-coordinating behaviour.
Metallkomplexe der diuretischen Droge Furosemid
Zusammenfassung Neue Komplexe der Verbindungen:M(fur)2·2H2O (M = Mn, Cu, Zn),M(fur)2·3H2O (M = Co, Ni, Cd), Hg2(fur)3Cl2·2H2O, Pd(fur)Cl·H2O und Rh(fur)3·3H2O, wobeifurH 4-chlor-N-(2-furfuryl)-5-sulfamoylanthanilsäure ist, wurden dargestellt. Die Komplexe wurden durch Leitfähigkeitsmessungen, Röntgen-Pulver-Aufnahmen, thermogravimetrische Analysen, Messungen des effektiven magnetischen Dipolemomentes sowie durch spektroskopische Untersuchungen (IR,1H-NMR und ESR) charakterisiert. Das Anionfur – zeigt das Verhalten einer Chelat-bidentat-O(carboxylato),N(imino)-Koordination.相似文献
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膜的动电特性研究中,往往采用流动电位方法。该方法中,Ag-Ag Cl测试电极的质量是影响测试准确性的关键要素。本文采用正交试验设计和方差分析,着重考察电解法制备Ag-Ag Cl电极过程中,电流强度(I)、氯化时间(t)、电解质溶液浓度(CHCl)、电极来源(n)、烘烤温度(T)、活化电极溶液浓度(CKCl)等因素对Ag-Ag Cl电极稳定性的影响。得到Ag-Ag Cl电极的最优制备参数为:电流密度3.0m A/cm2,氯化时间50min,盐酸浓度0.1mol·L-1,烘烤温度120℃,活化电极溶液(KCl)浓度0.001mol·L-1;最显著影响因素为电极来源,显著影响因素为氯化时间和烘烤温度。对最优条件组合下制备的AgAg Cl电极,进行了稳定性实验,结果表明:制备的电极具有较好的稳定性,24h内电极电位漂移量小于0.10mv,7天内电极电位漂移量小于0.2mv;在聚偏氟乙烯中空纤维超滤膜流动电位测试中,流动电位与流动压差具有良好的线性和可重复性,回归曲线R20.99,变化规律符合Helmholtz-Smoluehowski公式,可以较好满足膜的流动电位测试要求。 相似文献
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Rikkou M Manos M Tolis E Sigalas MP Kabanos TA Keramidas AD 《Inorganic chemistry》2003,42(15):4640-4649
Reaction of the non-oxo V(IV) species [V(IV)Cl(2)(L(OO))(2)] [L(OO) = acetylacetonate (acac(-)) or benzoylacetonate (bzac(-))] with a chelate nitrogen-donor ligand L(NN) in acetonitrile leads to the reduction of V(IV) to V(III) and the formation of the mononuclear V(III) compounds of the general formula [V(III)Cl(2)(L(OO))(L(NN))] (L(OO) and L(NN) are acac(-) and bipy for 1; acac- and 5,5'-me(2)bipy for 2; acac(-) and 4,4'-tb(2)bipy for 3; acac(-) and phen for 4; bzac(-) and bipy for 5; bzac(-) and phen for 6). The reduction of the V(IV) complexes was monitored by GC-MS and (1)H NMR spectroscopy. Both one- and two-dimensional (2D COSY and 2D EXSY) (1)H NMR techniques were used to assign the observed (1)H NMR resonances of 1-6 in CD(2)Cl(2) or CDCl(3) solution. It appeared that in solution these V(III) complexes form two isomers which are in equilibrium: cis-[V(III)Cl(2)(L(OO))(L(NN))] <==> trans-[V(III)Cl(2)(L(OO))(L(NN))]. 2D EXSY cross-peaks were clearly observed between bipy- and acac-hydrogen atoms of the two geometrical isomers of 1-3 as well as between bipy and acac(-) protons of the cis isomer, indicating a dynamic process that corresponds to cis-trans isomerization and a cis-cis racemization. The thermodynamic and kinetic parameters of the equilibrium between these two isomers were calculated for compounds 1 and 2 by using variable temperature (VT) NMR data. Both cis-trans isomerization and cis-cis racemization processes probably proceed with an intramolecular twist mechanism involving a trigonal prismatic transition state. Density functional calculations (DFT) also indicated such a rearrangement mechanism. 相似文献
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以4-氯-7-硝基苯并-2-氧杂-1,3-二唑、乙二胺和溴乙酸乙酯等为原料,合成4-氨基-7-硝基苯并-2-氧杂-1,3-二唑类衍生物(NBD-OEt),通过IR、NMR和MS对其进行结构表征。研究NBD-OEt的吸收光谱和荧光光谱性质,探讨其在H2O/EtOH(60/40, V/V) pH 7.40的HEPES缓冲体系中对Hg2 的响应,以及NBD-OEt与Hg2 的结合模式。结果表明, 随Hg2 的不断加入可诱使NBD-OEt在476nm的吸收峰红移至514nm,并有两个等吸收点(347nm、482nm);其荧光发射峰由536nm红移至559nm,且在525nm出现等发射点;通过Job plot法测定NBD-OEt与Hg2 以1:1的计量比结合。 相似文献
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The ultrasonic signals in long bones contain multiple guided modes which are mutual superposed.The velocities of guided waves in long bones are very sensitive to cortical thickness (CTh).In this paper,Hilbert-Huang transform(HHT) was proposed to analyze multi-mode guided waves,which can decompose superposed waves into many independent modes.Then the group velocity of each mode was obtained at corresponding frequency,which was compared with the results of short time Fourier transform(STFT).The CTh was also obtained by comparing with the theoretical calculation.The results showed that the experimental determined thickness was in agreement with the actual CTh,indicating that measuring the velocity of the guided mode can be used to estimate the CTh.The HHT is an effective method to identify multimode guided waves. 相似文献