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1.
Aqueous solutions of bismuth(III) nitrilotriacetates BiNta · 2H2O and M3Bi(Nta)2 ·nH2O (M = Na, K, Rb, Cs, NH4, CN3H6, n = 0–4) and the K[Bi(Edta)(Tu)2] complex (Edta4– is the anion of ethylenediaminetetraacetic acid, Tu is thiocarbamide) are studied by the 1H NMR method at room temperature in the pH interval from 2 to 11. The formation of two types of bismuth nitrilotriacetate complexes in solutions is established. They are characterized by the presence (type 1) or absence (type 2) of the Bi–N bond. Their ratio, depending on the composition and pH of the solution, is determined. The K[Bi(Edta)(Tu)2] compound in solutions occurs as one form. The pH values at which the substance begins to decompose are determined for each compound.  相似文献   

2.
Summary The reactions of some copper(II) salts with bis(1-pyrazolyl)methane, H2Cbpz, bis(3,5-dimethylpyrazolyl)methane, H2Cbdmpz, and tris(1-pyrazolyl)methane, HCtpz give the following solid complexes: CuLX2 · nH2O (L=H2Cbpz, H2Cbdmpz or HCtpz; X=Cl, Br, NO 3 , OAc, or 1/2 SO 4 2– and n=0, 1, 3 or 5) and CuL2X2 · nH2O (L=HCtpz, X= C, Br, NO 3 or ClO 4 and n=0 or 2). The complexes have been characterised by elemental analysis, visible and i.r. spectral measurements.The reactions of Cu(HCtpz)X2 · nH2O (X=Cl or Br) with acetylacetonate (acac), dialkyldithiocarbamate (S2CNMe 2 , S2CNEt 2 ) or poly(1-pyrazolyl)borate (H2Bbpz, HBtpz) in aqueous solutions lead to the displacement of HCtpz and the subsequent formation of neutral [Cu(acac)2], [Cu(S2CNR2)2], [Cu(H2Bbpz)2] and Cu(HBtpz)2 while the reaction with oxalate ion, C2O 4 2– yields a stable neutral solid compound, [Cu(HCtpz)(C2O4)].  相似文献   

3.
Conclusions The temperature dependences of the121,123Sb NQR spectral parameters forTl2SbF5, TlSbF4, NaSbF3NO3·H2O, and Sb2OF4·2CO(NH2)2 have been studied in the region 77–400 K, and anomalous behavior has been found for the asymmetry parameter of the electric field gradient tensor of antimony atoms in these compounds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 544–548, March, 1988.  相似文献   

4.
Summary The chelating behaviour of two biologically active ligands, pyridine-2-carboxaldehyde(4-phenyl) thiosemicarbazone(L1H) and pyridine-2-carboxaldehyde thiosemicarbazone(LH), towards FeIII, CoIII, FeII and RhIII has been investigated. The ligands act as tridentate N–N–S donors, resulting in the formation of bis-chelate complexes of the type MIII(A)2X·nH2O (A=L1 or L; X=Cl, ClO4; M=CoIII, RhIII, FeIII), FeII(L1H)2SO4·2H2O and FeII(L1)2·H2O. Biological activity of the ligands and the metal complexes in the form ofin vitro antibacterial activities towardsE. coli has been evaluated and the possible reasons for enhancement of the activity of ligands on coordination to metal ion is discussed.  相似文献   

5.
Summary Thirteen new complexes, MLX·nH2O and ML2(ClO4)2· nH2O [M = Co, Ni, Cu; X = Cl, Br, NO f3 p– , 1/2SO f4 p2– ; n = 1 or 2; and L = 2-(3,5-dimethylpyrazol-1-yl)benzothiazole], have been synthesized, and characterized by elemental analysis, conductivity measurements, magnetic moments, thermal studies and electronic, i.r. and e.p.r. spectral studies. On the basis of available data probable structures have been proposed. In a few cases the antibacterial and antifungal activities increase on complexation of the ligand with metals.  相似文献   

6.
Summary Different extraction sytems including long chain quaternary alkylammonium salts and APDC were investigated in order to determine the optimal conditions for extraction separation and preconcentration of traces of Ag, Bi, Cd, Cu, Fe, Mo, Pb, Sb and Zn from high purity NiSO4·6H2O, NiCl2·6H2O, Ni(OOCCH3)2·4H2O and Ni(NO)3)2·6 H2O. Best results for multielement preconcentration were found with the extraction system HCl-trioctylmethylammonium chloride-0,002 mol/l APDC/MIBK. The proposed method permits the flame atomic absorption determination of 5·10–6%, Ag, Cd, Cu and Zn, 1·10–5% Bi, Fe, Pb and 5·10–5% Mo and Sb with good accuracy and precision.  相似文献   

7.
Summary N-Cyano-N-methyl-N(2-[(5-methyl-1H-imidazol-4-yl)-methylthio] ethyl) guanidine cimetidine (CM), complexes with CoII, NiII and CuII are described. The compounds are of stoichiometry [M(CM)2]SO4 · nH2O [M = CoII, NiII or CuII; n = 3,3 or 4, respectively], [M(CM)2](ClO4)2 [M = CoII or NiII], [M(CM)2]Cl2 · nH2O [M=CoII, NiII or CuII; n = 1, 2, or 2, respectively] and [Cu(CM)SO4] · 2H2O. The electronic spectra of the compounds in solid state, magnetic susceptibilities and i.r. and e.p.r. spectra were studied. Octahedral environments are proposed for the complexes: [M(CM)2]SO4·nH2O, [M(CM)2](ClO4)2, [Ni(CM)2]Cl2 · 2H2O, [Cu(CM)2]Cl2 · 2H2O and [Cu(CM)SO4] · 2H2O and a tetrahedral structure for [Co(CM)2]Cl2 · H2O.  相似文献   

8.
Summary New complexes of the general formula M(L)3Cl3 and M(5-AInz)2Cl3 · n H2O (where M = RuIII, RhIII and IrIII; L = indazole and 5-nitroindazole; n=1–2) have been synthesized and characterised by elemental analysis, molar conductance, magnetic susceptibility and i.r. and electronic spectral measurements. All the complexes are covalent and apparently have an octahedral geometry. The ligands are monocoordinated through the pyrrole nitrogen. From the far i.r. spectra amer configuration has been assigned to the indazole and 5-nitroindazole complexes.  相似文献   

9.
Summary Complexes [NiL2]X2·nH2O (L=diethylenetriamine; n=O when X=CF3CO2 or CCl3CO2; n=1 when X=Cl or Br, and n=3 when X=0.5SO4 or 0.5SeO4) and NiLX2·nH2O (n=1 when X=Cl or Br; n=3 when X=0.5SO4 or 0.5SeO4) have been synthesised and investigated thermally in the solid state. NiLSO4 was synthesised pyrolytically in the solid state from [NiL2]SO4·[NiL2]X2 (X=Cl or Br) undergo exothermic irreversible phase transitions (242–282° C and 207–228° C; H=–11.3 kJ mol–1 and –1.9 kJ mol–1 for [NiL2]Cl2 and [NiL2]Br2, respectively). [NiL2]-phenomenon (158–185° C; H=2.0 kJ mol–1). NiLX2· nH2O (n=1 or 3) undergo simultaneous deaquation-isomerisation upon heating. All the complexes possess octahedral geometry.  相似文献   

10.
The extraction of Sb(III) chloride by nonpolar solvents from 0.15M HCl was studied as a function of sulphuric acid concentrations in the aqueous phase. The distribution of Sb(III) chloride between the nonpolar solvents benzene, toluene, xylene, nitrobenzene, cyclohexane, chloroform and carbon tetrachloride and filter paper is reported. In case of benzene the Sb(III) activity (given in counts·s–1·ml–1) decreases from 1500 to 200 after 24 hours. The corresponding values are about 1200 and 540 for toluene, 1330 and 50 for xylene, 1050 and 700 for nitrobezene, 1080 and 22 for cyclohexane, 330 and 30 for chloroform and 130 and 40 for carbon tetrachloride. More than 95% of the adsorbed Sb(III) is desorbed by 1M HNO3, 1M HCl or 0.5M H2SO4 by contacting the loaded filter paper with any of these acids for 27 hours.  相似文献   

11.
Triphenylantimony dibenzoate Ph3Sb(O2CPh)2, triphenylantimony bis(methylbenzoates) Ph3Sb(O2CC6H4Me-n)2 (n = 2, 4), and tri-p-tolylantimony bis(trichloacetate) p-Tol3Sb(O2CCCl3)2, whose Sb atoms have trigonal bipyramidal coordination, were studied using X-ray diffraction analysis. The Sb–O bond lengths are equal to 2.119(2) and 2.144(2); 2.115(2); 2.118(2) and 2.127(2); 2.133(2) Å, the Sb···O(=C) intramolecular contacts are equal to 2.797(2) and 2.698(2); 2.845(2); 2.814(2) and 3.030(2); 3.119(2) Å, respectively. The following correlation was found in the structures of triorganylantimony dicarboxylates: the shorter the Sb···O(=C) distances, the greater the equatorial angle on the side of the intramolecular contacts.  相似文献   

12.
Summary Complexes of chromium(III) with 2,5-diphenyloxazole (PPO) of general formula Cr(PPO)nX3·m H2O, where X=Cl, Br, I or NO 3 su– ; n=1–3 and m=0–6, have been prepared and studied by spectroscopic and magnetic methods and by molar conductivity measurements. All the complexes seem to be hexacoordinated, generally with monodentate N-bonded ligand.  相似文献   

13.
A capillary electrophoretic method was developed for the simultaneous determination of Sb(III) and Bi(III). A 1.0 mM W(VI)-0.10 mM P(V) complexing reagent readily reacted with a mixture of trace amounts of Sb(III) and Bi(III) to form the corresponding ternary Keggin-type complexes; [P(SbIIIW11)O40]6− and [P(BiIIIW11)O40]6− in 0.01 M malonate buffer (pH 2.4). Since the peaks due to the migrations of the ternary complex anions were well separated in the electropherogram, the pre-column complex-formation reaction was applied to the simultaneous CE determination of Sb(III) and Bi(III) with direct UV detection at 255 nm. The calibration curves were linear in the range of 2×10−7-5×10−5 M; a detection limit of 1×10−7 M was achieved for Sb(III) or Bi(III) (the signal-to-noise ratio=3).  相似文献   

14.
Triorganoantimony and Triorganobismuth Disulfonates. Crystal and Molecular Structure of (C6H5)3M(O3SC6H5)2(M = Sb, Bi) Triorganoantimony disulfonates R3Sb(O3SR′)2 [R = CH3 = Me, C6H5 = Ph; R′ = Me, CH2CH2OH, Ph, 4-CH3C6H4. R = Ph; R′ = 2,4-(NO2)2C6H3], Me3Sb(O3SCF3)2 · 2 H2O and triphenylbismuth disulfonates Ph3Bi(O3SR′)2 [R = Me, CF3, CH2CH2OH, Ph, 4-CH3C6H4, 2,4-(NO2)2C6H3] have been prepared by reaction of Me3Sb(OH)2, (Ph3SbO)2, and Ph3BiCO3, respectively, with the appropriate sulfonic acids. From vibrational data an ionic structure is inferred for Me3Sb(O3SCF3)2 · 2 H2O and Me3Sb(O3SCH2CH2OH)2, and a covalent structure for the other compounds with a penta-coordinated central atom with trigonal bipyramidal surrounding (Ph or Me in equatorial, unidentate sulfonate ligands in apical positions). Ph3M(O3SPh)2 (M = Sb, Bi) crystallize monoclinic [space group P21/c; M = Sb/Bi: a = 1 611.5(8)/1 557.4(9), b = 987.5(6)/1 072,5(8), c = 1 859.9(9)/1 696.5(9) pm, β = 105.71(5)/96.62(5)°; Z = 4; d(calc.) 1.556/1.781 Mg · m?3; Vcell = 2 849.2 · 106/2 814.8 · 106 pm3; structure determination from 3 438/3 078 independent reflexions (I ≥ 3σ(I)), R(unweighted) = 0.030/0.029]. M is bonding to three Ph groups in the equational plane [mean distances Sb/Bi? C:210.1(4)/219.1(7) pm] and two sulfonate ligands with O in apical positions [distances Sb? O: 210.6(3), 212.8(2); Bi? O: 227.6(5), 228.0(4) pm]. Weak interaction of M with a second O atom of one sulfonate ligand is inferred from a rather short M? O contact distance [Sb? O: 327.4(4), Bi? O: 312.9(5) pm], and from the distortion of equatorial angles [C? Sb? C: 128.4(2), 119.2(2), 112.2(2); C? Bi? C: 135.9(3), 117.8(3), 106.3(3)°]  相似文献   

15.
Summary Methods are described for quantitative extraction of arsenic(III), antimony(III) and bismuth(III) with potassium ethyl xanthate-carbon tetrachloride. The optimum acidity conditions are 0.1–0.2 M hydrochloric acid for arsenic, 1.8–2.5 M hydrochloric acid for antimony and pH 1.5–4.0 for bismuth. From the organic extracts arsenic and antimony are estimated by conventional iodometric methods while bismuth is determined spectrophotometrically at 400 nm. The effect of acidity, reagent concentration, period of extraction and diverse ions are discussed. The infra-red spectra are also described.
Zusammenfassung Verfahren für die Extraktion von As(III), Sb(III) und Bi(III) mit Kaliumäthylxanthat/Tetrachlorkohlenstoff werden beschrieben. Die optimalen Aciditätsbedingungen sind: 0,1–0,2 M HCl für As, 1,8–2,5 M HCl für Sb und pH 1,5–4,0 für Bi. As und Sb werden nach Entfernung des organischen Lösungsmittels jodometrisch bestimmt; Bi wird im gelb gefärbten Extrakt spektrophotometrisch bei 400 nm bestimmt. Der Einflu\ der Acidität, der Reagenskonzentration, der Schütteldauer und verschiedener Fremdionen auf die Extraktion wird besprochen. Die IR-Spektren der gebildeten Komplexe werden diskutiert.
  相似文献   

16.
Potassium pentafluorobismuthate(III), nitrate-chloride BiIII complexes MBiCl3NO3 (M=K, (NH2)2CNH2), sulfate-chloride BiIII complexes MBiCl2SO4 (M=K, Rb, NH4, (NH2(2CNH2), and BiIII complexonates with the anions of ethylenediaminetetraacetic acid M[Bi(edta)]2·nH2O (M=Mg, Ca, Ni, Cd) and nitrilotriacetic acid Bi(nta)·2H2O, and Bi(nta)·3thio·H2O (thio is thiourea) were studied by209Bi NQR spectroscopy. A second-order phase transition was observed in K2BiF5 at 100 K. The compounds Bi(nta)·2H2O, (NH2)2CNH2BiCl3NO3, and MBiCl2SO4 (M=K, NH4) are piezoelectrics. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2237–2240, November, 1998.  相似文献   

17.
Antimony(m) chlorofluoride complexes M2SbCl3F2 (M = Rb, Cs, or NH4) were studied by the121,123Sb NQR method. A temperature range (77–285 K) with anomalous change in the NQR parameters and a second-order phase transition at 250–280 K for (NH4)2SbCl3F2 were found.Translated from Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 382–385, February, 1996  相似文献   

18.
Summary 1. A study of the reaction of sodium and potassium metaniobates with hydrogen peroxide at 0° showed that for low H2O2 concentrations (3–6%) peroxide compounds of niobium are formed Na(K)NbO4· nH2O (n=1.5–3.5). With high H2O2 concentrations (10–54%) the compounds formed are not those described in the literature but more soluble peroxide compounds of the perhydrate type Na(K)NbO4-nH2O2· mH2O (n=1.3–1.5; m =1.5-3), rather unstable at 0°.At –10° the perhydrates of permetaniobates form in a more stable form and with a higher content of active oxygen (11–12.3%); they were separated and studied in the solid state.  相似文献   

19.
Inhaltsübersicht. Triorganoantimon- und Triorganobismutdicarboxylate R3M[O2C(CH2)n-2-C4H3X]2 (M = Sb, R = CH3, C6H11, C6H5, 4-CH3OC6H4; M = Bi, R = C6H5, 4-CH3C6H4; n = 0, X = O, S, NH, NCH3. M = Sb, R = CH3, C6H5; M = Bi, R = C6H5; n = 1, X = O, S. M = Sb, R = C6H11, n = 1, X = S; R = 4-FC6H4, n = 0, X = O, S, NCH3; R = 2,4,6-(CH3)3C6H2, n = 0, X = O, S, NH) wurden durch Reaktionen von R3Sb(OH)2 (R = CH3, C6H11, 2,4,6-(CH3)3C6H2), R3SbO (R = C6H5, 4-CH3OC6H4, 4-FC6H4) bzw. R3BiCO3 mit den entsprechenden fünfgliedrigen heterocyclischen Carbonsäuren 2-C4H3X(CH2)nCOOH dargestellt. Auf der Basis schwingungsspektroskopischer Daten wird für alle Verbindungen eine trigonal bipyramidale Umgebung vom M (zwei O-Atome von einzähnigen Carboxylatliganden in den apikalen, drei C-Atome von R in den äquatorialen Positionen) vorgeschlagen, ferner eine schwache Wechselwirkung zwischen O(=C) jeder Carboxylatgruppe und M. Die Kristallstrukturbestimmung von (C6H5)3Sb(O2C–2-C4H3S)3 stützt diesen Vorschlag. Die Verbindung kristallisiert triklin [Raumgruppe P$1; a = 891,8(14), b = 1058,2(12), c = 1435,6(9) pm, α = 68,53(8), β = 85,47(9), γ = 85,99(11)°; Z = 2; d(ber.) = 1,607 Mg m–3; V(Zelle) = 1255,6 Å3; Strukturbestimmung anhand von 3947 unabhängigen Reflexen (Fo > 3σ(F2o)), R(ungewichtet) = 0,037]. Sb bindet drei C6H5-Gruppen in der äquatorialen Ebene [mittlerer Abstand Sb–C: 211,1(5)pm] und zwei einzähnige Carboxylatliganden in den apikalen Positionen einer verzerrten trigonalen Bipyramide [mittlerer Abstand Sb–O: 212,0(4) pm]. Aus den relativ kurzen Sb – O(=C)-Abständen [274,4(4) und 294,9(4) pm] und aus der Aufweitung des dem O(=C)-Atom nächsten äquatorialen C–Sb–C-Winkels auf 145,9(2)° [andere C-Sb-C-Winkel: 104,4(2), 109,5(2)°] wird auf schwache Sb–O(=C)-Koordination geschlossen. Schließlich wird eine Korrelation zwischen dem (+, –)I-Effekt des Organoliganden R an M (M = Sb, Bi) und der Stärke der M–O(=C)-Koordination in den Dicarboxylaten R3M[O2C(CH2)n–2-C4H3X]2 vorgeschlagen. Triorganoanümony and Triorganobismuth Derivatives of Carbonic Acids of Five-membered Heterocycles. Crystal and Molecular Structure of (C6H5)3Sb(O2C–2-C4H3S)2 Triorganoantimony- and triorganobismuth dicarboxylates R3M[O2C(CH2)n–2-C4H3X]2 (M = Sb, R = CH3, C6H11, C6H5, 4-CH3OC6H4; M = Bi, R = C6H5, 4-CH3C6H4; n = 0, X = O, S, NH, NCH3. M = Sb, R = CH3, C6H5; M = Bi, R = C6H5; n = 1, X = O, S. M = Sb, R = C6H11, n = 1, X = S; R = 4-FC6H4, n = 0, X = O, S, NCH3; R = 2,4,6-(CH3)3C6H2, n = 0, X = O, S, NH) have been prepared by reaction of R3Sb(OH)2 (R = CH3, C6H11; 2,4,6-(CH3)3C6H2), R3SbO (R = C6H5, 4-CH3OC6H4, 4-FC6H4) or R3BiCO3 with the appropriate five-membered heterocyclic carboxylic acid. From vibrational data for all compounds a trigonal bipyramidal environment around M (two O atoms of unidendate carboxylate ligands in apical, three C atoms (of R) in equatorial positions) is proposed and also an additional weak interaction of O(=C) of each carboxylate group and M. The crystal structure determination of Ph3Sb(O2C–2-C4H3S)2 gives additional prove to this proposal. It crystallizes triclinic [space group P$1; a = 891.8(14), b = 1058.2(12), c = 1435.6(9) pm, α = 68.53(8), β = 85.47(9), γ = 85.99(11)°; Z = 2; d(calc.) = 1.607 Mg m–3; Vcell = 1255.6 Å3; structure determination from 3 947 independent reflexions (Fo > 3σ(F2o)), R(unweighted) = 0.037]. Sb is bonding to three C6H5 groups in the equatorial plane [mean distance Sb–C: 211.1(5) pm] and two unidentate carboxylate ligands in the apical positions of a distorted trigonal bipyramid [mean distance Sb–O: 212.0(4) pm]. From the relatively short Sb–O(=C) distances [274.4(4) and 294.9(4) pm] and from the enlarged value of the equatorial C–Sb–C angle next to the O(=C) atom [145.9(2)°; other C–Sb–C angles: 104.4(2), 109.5(2)°] additional weak Sb–O(=C) coordination is inferred. Finally a correlation between the (+, –) I-effect of the organic ligands It at M and the strength of the M–O = C interaction is suggested.  相似文献   

20.
Summary The activities of the diethylenetriaminemonoacetatocobalt(III) complexes, [Co(en)(DTMA)]I2, [CoX2(DTMA)] and [CoCO3(DTMA)]·H2O (DTMA=diethylenetriaminemonoacetato or formally 3-amino-3, 6-diazaoctanato; en=ethylenediamine, X=Cl, NO 2 , NCS) were studied onEscherichia coli B growing in a minimal glucose medium in both lag- and log-phases. Activities decrease in the order: [Co(NCS)2(DTMA)]> [Co(NO2)2(DTMA)]>[Co(en)(DTMA)]I2>[CoCl2(DTMA)] >[CoCO3(DTMA)]·H2O. The antagonistic activities of the complexes were also studied.  相似文献   

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