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1.
4-(Chloroacetyl)diphenyl thioether (1) was synthesized from chloroacetyl chloride and diphenyl thioether in the presence of AlCl3 as catalyst in a Friedel-Crafts reaction. Subsequently, its keto oxime (2) and glyoxime (3) derivatives were prepared. N-(4′-Benzo[15-crown-5]thiophenoxyphenylaminoglyoxime (H2L) and its sodium chloride complex (H2L · NaCl) were prepared from 4-(thiophenoxy)chlorophenylglyoxime (3), 4′-aminobenzo[15-crown-5] and sodium bicarbonate or sodium bicarbonate and sodium chloride. Ni(II), Co(II) and Cu(II) complexes of H2L and H2L · NaCl have a metal–ligand ratio of 1:2 and the ligand coordinates through the two N atoms, as do most of the vic-dioximes. The BF2-capped Ni(II) mononuclear complex of the vic-dioxime was prepared. The macrocyclic ligands and their transition metal complexes were characterized on the basis of FT-IR, 1H NMR, 13C NMR spectroscopy and elemental analyses data.  相似文献   

2.
N′-(4′-Benzo[15-crown-5]naphthylaminoglyoxime (H2L) and its sodium chloride complex (H2L·NaCl) have been prepared from 2-naphthylchloroglyoxime, 4′-aminobenzo[15-crown-5] and sodium bicarbonate or sodium bicarbonate and sodium chloride. Nickel(II), cobalt(II) and copper(II) complexes of H2L and H2L·NaCl have a metal–ligand ratio of 1:2 and the ligand coordinates through the two N atoms, as do most of the vic-dioximes. The BF 2 + -capped Ni(II), Co(III) and mononuclear complexes of thevic-dioxime were prepared. The macrocyclic ligands and their transition metal complexes have been characterized on the basis of IR, 1H NMR spectroscopy and elemental analyses data.  相似文献   

3.
N-(4-Benzo[15-crown-5])biphenylaminoglyoxime (H2L) and sodium chloride salt of N-(4-benzo[15-crown-5])biphenylaminoglyoxime (H2L · NaCl) have been prepared from 4-biphenylchloroglyoxime, 4-aminobenzo[15-crown-5], and sodium bicarbonate and sodium chloride. Nickel(II), cobalt(II), and copper(II) complexes with H2L and H2L · NaCl have a metal–ligand ratio of 1 : 2 and the ligand coordinates through the two N atoms, as do most of the vic-dioximes. Their IR spectra and elemental analyses are given, together with 1H NMR spectra of the ligands.  相似文献   

4.
N'-[4'-benzo(15-crown-5)]-4-tolylaminoglyoxime (H2L1),the sodium chloride salt of H2L1 (H2L1...NaCl),N'-[4'-benzo(15-crown-5)]-4-chlorophenylaminoglyoxime(H2L2) and the sodium chloride salt of H2L2 (H2L2...NaCl)have been prepared from p-chlorophenylchloroglyoxime,p-tolylchloroglyoxime, 4'-aminobenzo[15-crown-5] and sodiumbicarbonate or sodium bicarbonate and sodium chloride. Nickel (II),cobalt (II) and copper (II) complexes of H2L and H2L...NaClhave a metal-ligand ratio of 1 : 2 and the ligand coordinatesthrough the two N atoms, as do most of the vic-dioximes. Their IR spectra and elemental analyses are given, together with1H NMR spectra of the ligands.  相似文献   

5.
The complexation reactions between Mg2+,Ca2+,Sr2+ and Ba2+ metal cations with macrocyclic ligand, dicyclohexano-18-crown-6 (DCH18C6) were studied in methanol (MeOH)–water (H2O) binary mixtures at different temperatures using conductometric method . In all cases, DCH18C6 forms 1:1 complexes with these metal cations. The values of stability constants of complexes which were obtained from conductometric data show that the stability of complexes is affected by the nature and composition of the mixed solvents. While the variation of stability constants of DCH18C6-Sr 2+ and DCH18C6-Ba2+versus the composition of MeOH–H2O mixed solvents is monotonic, an anomalous behavior was observed for variations of stability constants of DCH18C6-Mg2+ and DCH18C6-Ca2+ versus the composition of the mixed solvents. The values of thermodynamic parameters (ΔHc°, ΔSc°) for complexation reactions were obtained from temperature dependence of formation constants of complexes using the van’t Hoff plots. The results show that in most cases, the complexation reactions are enthalpy stabilized but entropy destabilized and the values of thermodynamic parameters are influenced by the nature and composition of the mixed solvents. The obtained results show that the order of selectivity of DCH18C6 ligand for metal cations in different concentrations of methanol in MeOH–H2O binary system is: Ba2+>Sr2+>Ca2+> Mg2+.  相似文献   

6.
The reaction of the heteroleptic Nd(III) iodide, [Nd(L′)(N″)(μ-I)] with the potassium salts of primary aryl amides [KN(H)Ar′] or [KN(H)Ar*] affords heteroleptic, structurally characterised, low-coordinate neodymium amides [Nd(L′)(N″)(N(H)Ar′)] and [Nd(L′)(N″)(N(H)Ar*)] cleanly (L′ = t-BuNCH2CH2[C{NC(SiMe3)CHNt-Bu}], N″ = N(SiMe3)2, Ar′ = 2,6-Dipp2C6H3, Dipp = 2,6-Pri2C6H3, Ar* = 2,6-(2,4,6-Pri3C6H2)2C6H3). The potassium terphenyl primary amide [KN(H)Ar*] is readily prepared and isolated, and structurally characterised. Treatment of these primary amide-containing compounds with alkali metal alkyl salts results in ligand exchange to give alkali metal primary amides and intractable heteroleptic Nd(III) alkyl compounds of the form [Nd(L′)(N″)(R)] (R = CH2SiMe3, Me). Attempted deprotonation of the Nd-bound primary amide in [Nd(L′)(N″)(N(H)Ar*)] with the less nucleophilic phosphazene superbase ButNP{NP(NMe2)3}3 resulted in indiscriminate deprotonations of peripheral ligand CH groups.  相似文献   

7.
Two new coordination complexes, viz. [Co(tmb)2(4,4′-bpy)2(H2O)2](Htmb)2 (1) and {[Ni(tmb)2(μ-4,4′-bpy)2(H2O)2](4,4′-bpy)}n (2), have been hydrothermally synthesized by reaction of the corresponding metal acetate with 2,4,6-trimethylbenzoic acid (Htmb) and 4,4′-bipyridyl (4,4′-bpy). X-ray single-crystal diffraction suggests that complex 1 represents a discrete mononuclear species in which the central metal ion is coordinated by the terminal carboxylate moiety and the 4,4′-bipyridyl ligand. The crystal structure of complex 2 reveals a 1D chain coordination polymer in which the Ni(II) ions are connected by the bridging 4,4′-bipyridyl ligands. In both cases, the coordination arrays are further extended via hydrogen bonding interactions to generate 3D supramolecular networks. Complexes 1 and 2 have also been characterized by spectroscopic (IR and UV/Vis), thermal (TGA) and magnetic susceptibility measurements. In addition, both complexes exhibit antimicrobial activity.  相似文献   

8.
Assembly of 5-sulfosalicylic acid (H3L) and d10 transition metal ions (CdII, AgI) with the neutral N-donor ligands produces five new complexes: [Cd2(HL)2(4,4′-bipy)3]n·2nH2O (1), {[Cd2(μ2-HCO2)2(4,4′-bipy)2(H2O)4][Cd(HL)2(4,4′-bipy)(H2O)2]}n (2), {[Cd(4,4′-bipy)(H2O)4][HL]·H2O}n (3), [Cd(HL)(dpp)2(H2O)]n·4nH2O (4), {[Ag(4,4′-bipy)][Hhbs]}n (5) (4,4′-bipy=4,4′-bipyridine, dpp=1,3-di(pyridin-4-yl)propane, H2hbs=4-hydroxybenzenesulfonic acid, the decarboxylation product of H3L). Complex 1 adopts a 5-connected 3D bilayer topology. Complex 2 has the herring-bone and ladder chain, which are extended to a 3D network via hydrogen bonding. In 3–4 complexes, 3 is a 3D supermolecular structure formed by polymeric chains and 2D network of HL2−, while 4 gives the double-stranded chains. In 5, ladder arrays are stacked with the 2D networks of Hhbs anions in an –ABAB– sequence. Complexes 1–4 display green luminescences in solid state at room temperature, while emission spectra of 3 and 4 show obvious blue-shifts at low temperature.  相似文献   

9.
Solubility studies of TcO2· xH2O(am) have been conducted as a function of H+ concentration from 1 × 10– 5 to 6 M HCl and as a function of chloride concentration from 1 × 10– 3 to 5 M NaCl. These experiments were conducted under carefully controlled reducing conditions such that the preponderance of Tc present in solution is in the reduced oxidation state and was determined to be Tc(IV) by XANES analysis. The aqueous species and solid phases were characterized using a combination of techniques including thermodynamic analyses of solubility data, XRD, and XANES, EXAFS, and UV-vis spectroscopies. Chloride was found to significantly affect Tc(IV) concentrations through (1) the formation of Tc(IV) chloro complexes [i.e., TcCl4(aq) and TcCl6 2 –] and a stable compound [data suggests this compound to be TcCl4(am)] in highly acidic and relatively concentrated chloride solutions, and (2) its interactions with the positively charged hydrolyzed Tc(IV) species in solutions of relatively low acidity and high chloride concentrations. A thermodynamic model was developed that included hitherto unavailable chemical potentials of the Tc(IV)–chloro species and Pitzer ion-interaction parameters for Tc(IV) hydrolyzed species with bulk electrolyte ions used in this study. The thermodynamic model presented in this paper is consistent with the extensive data reported in this study and with the reliable literature data and is applicable to a wide range of H+ and Cl concentrations and ionic strengths.  相似文献   

10.
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   

11.
The infrared spectra, in the 700–200 cm–1 region, have been reported for6LiHCO2 · H2O,6LiHCO2 · D2O,7LiHCO2 · H2O and7LiHCO2 · D2O and the observed fundamental bands have been discussed taking into account the6Li/7Li and H2O/D2O isotope wavenumber shifts on the fundamental vibrations.
Infrarotspektren (700–200 cm–1) und6Li/7Li- und H2O/D2O-Isotopeneffekte für vier isotopensubstituierte Lithiumformat-monohydrate
Zusammenfassung Die Infrarotspektren in der Region von 700–200 cm–1 werden für6LiHCO2 · H2O,6LiHCO2 · D2O,7LiHCO2 · H2O und7LiHCO2 · D2O angegeben und die beobachteten Grundschwingungen zusammen mit den isotopischen Verschiebungen der Wellenzahlen diskutiert.
  相似文献   

12.
New Schiff base (H2L) ligand is prepared via condensation of o-phthaldehyde and 2-aminophenol. The metal complexes of Cr(III), Mn(II), Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with the ligand are prepared in good yield from the reaction of the ligand with the corresponding metal salts. They are characterized based on elemental analyses, IR, solid reflectance, magnetic moment, electron spin resonance (ESR), molar conductance, 1H NMR and thermal analysis (TGA). From the elemental analyses data, the complexes are proposed to have the general formulae [M(L)(H2O)nyH2O (where M = Mn(II) (n = 0, y = 1), Fe(II) (n = y = 0), Co(II) (n = 2, y = 0), Ni(II) (n = y = 2), Cu(II) (n = 0, y = 2) and Zn(II) (n = y = 0), and [MCl(L)(H2O)]·yH2O (where M = Cr(III) and Fe(III), y = 1–2). The molar conductance data reveal that all the metal chelates are non-electrolytes. IR spectra show that H2L is coordinated to the metal ions in a bi-negatively tetradentate manner with ONNO donor sites of the azomethine N and deprotonated phenolic-OH. This is supported by the 1H NMR and ESR data. From the magnetic and solid reflectance spectra, it is found that the geometrical structures of these complexes are octahedral (Cr(III), Fe(III), Co(II) and Ni(II) complexes), tetrahedral (Mn(II), Fe(II) and Zn(II) complexes) and square planar (Cu(II) complex). The thermal behaviour of these chelates is studied and the activation thermodynamic parameters, such as, E*, ΔH*, ΔS* and ΔG* are calculated from the DrTGA curves using Coats-Redfern method. The parent Schiff base and its eight metal complexes are assayed against two fungal and two bacterial species. With respect to antifungal activity, the parent Schiff base and four metal complexes inhibited the growth of the tested fungi at different rates. Ni(II) complex is the most inhibitory metal complex, followed by Cr(III) complex, parent Schiff base then Co(II) complex. With regard to bacteria, only two of the tested metal complexes (Mn(II) and Fe(II)) weakly inhibit the growth of the two tested bacteria.  相似文献   

13.
Two new complexes, [Cu(L1){N(CN)2}]·ClO4 (1) (L1 is 1,8-dimethyl-1,3,6,8,10,13-hexa-azacyclotetradecane) and [Co(L2)(N3)2]·ClO4 (2) (L2 is 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetra-azacyclotetradecane) have been synthesized and characterized. The compounds crystallize in the monoclinic system P21 space group for 1 and P21/n for 2. Single crystal X-ray analysis reveals that the compound 1 assumes a one-dimensional structure via hydrogen-bonding interactions, in which each Cu(II) ion is coordinated by four nitrogen atoms from ligand L1 and one nitrogen atom from [N(CN)2] anion. For compound 2, each Co(III) ion is coordinated by four nitrogen atoms of ligand L2 and two nitrogen atoms from N3 anion.  相似文献   

14.
The crystal and molecular structures of the [PrIII(nta)(H2O)2]·H2O (nta = nitrilotriacetic acids), K3[GdIII(nta)2(H2O)]·6H2O, and K3[YbIII(nta)2]·5H2O complexes have been determined by single-crystal X-ray structure analyses. In [PrIII(nta)(H2O)2]·H2O, the PrIIINO8 part forms a nine-coordinate pseudo-monocapped square antiprismatic structure in which one N and three O atoms are from one nta ligand in the same molecule, three O atoms from another nta ligand in the neighboring molecule and two O atoms from two coordinate water molecules. In K3[GdIII(nta)2(H2O)]·6H2O, the [GdIII(nta)2(H2O)3- complex anion has a nine-coordinate pseudo-monocapped square antiprismatic structure in which each nta acts as a tetradentate ligand with one N atom of the amino group and three O atoms of the carboxylic groups. In K3[YbIII(nta)2]·5H2O, each nta also acts as a tetradentate ligand with one N atom of amino group and three O atoms of the carboxylic groups, but the [YbIII(nta)2 3- complex anion has an eight-coordinate structure with a distorted square antiprismatic prism. All the results including those for [TmIII(nta)(H2O)2]·2H2O confirm the inferences on the coordinate structures and coordination numbers of rare earth metal complexes with the nta ligand.  相似文献   

15.
The enthalpies of solution of NaRb[B4O5(OH)4]·4H2O in approximately 1 mol dm−3 aqueous hydrochloric acid and of RbCl in aqueous (hydrochloric acid + boric acid + sodium chloride) were determined. From these results and the enthalpy of solution of H3BO3 in approximately 1 mol dm−3 HCl(aq) and of sodium chloride in aqueous (hydrochloric acid + boric acid), the standard molar enthalpy of formation of −(5128.02 ± 1.94) kJ mol−1 for NaRb[B4O5(OH)4]·4H2O was obtained from the standard molar enthalpies of formation of NaCl(s), RbCl(s), H3BO3(s) and H2O(l). The standard molar entropy of formation of NaRb[B4O5(OH)4]·4H2O was calculated from the Gibbs free energy of formation of NaRb[B4O5(OH)4]·4H2O computed from a group contribution method.  相似文献   

16.
19F, 11B, and 29Si NMR spectroscopy was used to examine the behavior of the guest–host complexes (BF3· H2O)2· 18-crown-6 · 2H2O, (BF3· H2O)2· DCH-6B, and (DCH-6A · H3O)SiF5in acetone (DCH-6B and DCH-6A are the cis-anti-cis- and cis-syn-cis-isomers of dicyclohexano-18-crown-6, respectively). It was shown that molecular boron fluoride complexes undergo partial solvolysis in acetone to yield BF3· acetone as the main product; the ionic pentafluorosilicate complex does not experience significant solvolysis transformations.  相似文献   

17.
New cadmium(II) complexes with phosphine telluride ligands of the type CdX2(R3PTe)n [X?=?ClO4?, n?=?4: R?=?n-Bu (1), Me2?N (2), C5H10?N (3), C4H8?N (4) or OC4H8?N (5); X?=?Cl, n?=?2: R?=?n-Bu (6), Me2?N (7), C5H10?N (8), C4H8?N (9) or OC4H8?N (10)] have been synthesized and characterized by elemental analyses, IR and multinuclear (31P, 125Te, and 113Cd) NMR spectroscopy. In particular, the solution structures of these complexes were confirmed by 113Cd NMR at low temperature, which displays a quintuplet for each of the perchlorate complexes and a triplet for each of the chloride complexes due to coupling with four and two equivalent phosphorus atoms, respectively, indicating a four-coordinate tetrahedral geometry for the metal center. These multiplet features were further accompanied by one bond Te–Cd couplings, clearly showing that the ligand is coordinated to the metal through tellurium. The results are discussed and compared with those obtained for closely related phosphine chalcogenide analogs.  相似文献   

18.
Summary Transition metal(II) chloro complexes of the new Schiff base ligand 1,2-bis(2-pyridylmethyleneimino)benzene (L), derived from 2-pyridinecarboxaldehyde and 1,2-phenylenediamine, were prepared. Compounds of [MnLCl2]-H2O, [CoLCl2]·2H2O, [NiLCl2] and [Zn3L2Cl4]Cl2 were prepared. Details are given of the formation of the complex [Cu(L·EtOH)Cl2], in which one molecule of EtOH adds across only one of the Schiff base {ie531-01} groups to give the coordinated ligand L·EtOH. The rationalization of this type of reaction by considering the steric requirements of the ligand is given. The complexes were characterized by elemental analyses, conductivity measurements, thermal techniques, mass spectra, magnetic susceptibilities and spectroscopic (i.r., ligand field, e.s.r., 1H n.m.r.) studies. The nitrogen donor atoms of the tetradentate ligands L and L·EtOH are assumed to adopt an essentially planar arrangement about manganese(II), cobalt(II), nickel(II) and copper(II), with the remaining axial coordination sites occupied by chloro ligands to yield high-spin octahedral molecules. A trinuclear structure, based on tetrahedrally coordinated metal ions, is proposed for the zinc(II) complex.  相似文献   

19.
A novel O—N—N—O-type tetradentate ligand H4mda (H4mda = malamido-N,N-diacetic acid) and the corresponding square-planar copper(II) complexes have been prepared and characterized. The mda4– ligand coordinates to the copper(II) ion via two pairs of deprotonated ligating atoms (two carboxylate oxygens and two deprotonated amide nitrogens) with in-plane square chelation. A four-coordinate, square-planar geometry has been established crystallographically for the [Co(H2O)6][Cu(mda)] · 2H2O complex. Structural data correlating the square-planar geometry of the [Cu(mda)]2– unit are discussed in relation to information obtained for similar complexes. The i.r., electronic, absorption and reflectance spectra of the complexes are analysed in comparison with related complexes of known geometries.  相似文献   

20.
Reactions of 1,2-di(o-aminophenylthio)ethane with 3-ethoxy-2-hydroxybenzaldehyde yield the new hexadentate N2S2O2 donor thioether Schiff base 1,2-bis(2-((2-(thio)phenylimino)methyl)-6-ethoxyphenol)ethane (H2L). Ni(II), Zn(II), Cd(II), and Hg(II) complexes of this ligand were prepared. Of these complexes, [NiL]·2H2O has been structurally characterized by X-ray crystallography. The coordination geometry around Ni(II) was described as octahedral. Zn(II), Cd(II), and Hg(II) complexes and the Schiff base ligand have been characterized by CHN analyses, molar conductivity, UV–vis, FT-IR, 1H, and 13C NMR spectroscopy.  相似文献   

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