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1.
The synthesis, crystal structures, and luminescent properties of two new complexes containing tetrazolyl ligands are described. Refluxing a mixture of fipronil (fipronil = (±)-5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile), sodium azide, and CuCl2 in ethanol and water gives complex 1, [M(L)2](H2O)2] ? 2H2O (HL = (±)-5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-tetrazole, M = Cu). Hydrothermal reaction of fipronil, sodium azide, and Cd(ClO4)2 in the presence of water and ethanol (Demko–Sharpless tetrazole synthesis) yields 2, [M(L)2](H2O)2] ? 2H2O (M = Cd). The metals in both complexes are six coordinate from two water molecules, two nitrogens from different tetrazolyl groups, and two nitrogens from pyrazolyl groups. Photoluminescence studies reveal that 2 exhibits strong blue fluorescent emission at λ max = 451 nm in solid state at room temperature.  相似文献   

2.
The neutral distorted octahedral complexes [ReOCl(L)] {H2L = N,N-bis(2-hydroxybenzyl)-2-(2-aminoethyl)dimethylamine (H2had); N,N-bis(2-hydroxybenzyl)-aminomethylpyridine (H2hap); N,N-bis(2-hydroxybenzyl)-2-(2-aminoethyl)pyridine (H2hae)} were prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H2L in ethanol. X-ray structure determinations of [ReOCl(had)] (1) and [ReOCl(hap)] (2) were performed, and the structures compared. In both complexes the choride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen.  相似文献   

3.

Monooxo complexes of rhenium(V) with 2-aminophenol and some of its derivatives (H2nod), containing the N,O donor-atom set, have been synthesized. Square-pyramidal complexes [ReO(nod)2]? were isolated by reaction with (n-Bu4N) [ReOCl4] in ethanol. In benzene the neutral species [ReOCL(Hnod)2] were obtained. In the presence of hydrochloric acid in ethanol, the anionic complexes (n-Bu4N) [ReOCl3(Hnod)] were produced. Trans-[ReOCl3(PPh3)2] was also reacted with some of the H2nod ligands to yield [ReOCL2(Hnod)(PPh3]. The crystal structure of [ReOCl2(Hmap)(PPh3)] (H2map = 2-aminobenzylalcohol) was determined; crystals are monoclinic, P21/n, with a = 15.065(6), b = 11.253(7), c = 15.850(7) Å, β = 94.27(4)°, U = 2680(2) &Aringsup3; and Z = 4. The structure was solved by the Patterson method and refined by full-matrix least-squares techniques to R = 0.042. The monoanionic Hmap? ligand is coordinated as a bidentate through a neutral amino nitrogen and an anionic alcoholate oxygen atom, with the latter trans to the oxo group.  相似文献   

4.
A series of mononuclear salen type copper(II) complexes, [CuLn] (n = 1–4), and their corresponding tetrahydrosalen complexes, [CuH2Ln] (n = 1,2) were prepared by the reaction of the N2O2 ligands with Cu(II) ion in ethanol, where H2L1 = N,N-bis(3,5-di-tert-butylsalicylidene)-2,2-dimethyle-1,3-diaminopropan, H2L2 = N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-diaminopropane, H2L3 = N,N-bis(4-methoxysalicylidene)-2,2-dimethyle-1,3-diaminopropan; H2L4 = N,N-bis(4-methoxysalicylidene)-1,2-diaminopropane, H2[H2L1] = N,N-bis(2-hydroxyl-3,5-di-tert-butylphenyl)-2,2-dimethyle-1,3-diaminopropan and H2[H2L2] = N,N-bis(2-hydroxyl-3,5-di-tert-butylphenyl)-1,2-diaminopropane. The prepared ligands and complexes were characterized by the combination of IR, UV-Vis, NMR (as far as possible), elemental and thermal analyses. All prepared compounds were also evaluated for their antibacterial (Escherichia coli and Staphylococcus aureus) and antifungal (Candida albicans) activities by the disc diffusion method. The compounds were found have no remarkable antimicrobial activities.  相似文献   

5.

Two novel macroacylic Schiff base ligands were prepared by condensation of two diamine metal complexes, [Ni(1,2-pn)2Cl2]·3H2O and [Cu(1,2-pn)2]SO4·2H2O with o-acetoacetylphenol. The ligands MH6L(M = Ni or Cu) are hexabasic and contain two O4 coordination sites. They act as ligands towards transition metal ions yielding homo- and heteronuclear complexes of the type [NiH4 LCu(H2O)2]·4H2O, [MH2LM' 2(H2O)6], [MLM' 4(H2O)8], [MH2 LCe2(NO>3)2(H2O)2] and [NiLTh2(NO3)2(H2O)2] (M = Ni or Cu; M' = Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Ce(III), Th(IV) and UO2 (VI)). The complexes were characterized by elemental analysis, thermogravimetric analysis (TGA), IR, visible and ESR spectra, magnetic susceptibility measurements and mass spectrometry. Magnetic moments were altered by the introduction of metal cations besides the one already present in the complex ligands. The M' cations were linked to two ketonic oxygen atoms and two phenyl oxygen atoms in [NiH6 L(H2O)2] and [CuH6 L] complex ligands. All homo- and hetero-, bi- and tri-nuclear complexes show antiferromagnetic interactions which are attributed to inter- or intramolecular interactions of the metal cations. Mass spectra of the complex ligands and selected homo- and heteronuclear complexes support the formula weights of these complexes. Visible and ESR spectra as well as magnetic moments indicated that the parent mononuclear complex ligands [MH6 L] have an octahedral geometry for Ni(II) and a square-planar geometry distorted towards tetrahedral for Cu(II). The metal cations in bi-, tri- and pentanuclear complexes are octahedral or square-planar. The octahedral configuration is completed by chloride anions and/or solvent molecules.  相似文献   

6.
The coordination behaviour of the diorganotin (IV) compounds R2SnCl2 (where R = Me, Ph) with 4H-pyrido [1,2-a] pyrimidin-4-one derivatives (L) has been described. The complexes R2SnCl2 · L obtained have been characterized physicochemically and spectroscopically. The pyrimidin-4-one ligands were found to coordinate with R2SnCl2 species in a monodentate fashion, mainly via the oxygen atom of the 4-one group or possibly via the nitrogen atom of the (SINGLE BOND)C(DOUBLE BOND)N linkage (the less sterically hindered nitrogen of the pyrimidine derivative) to give pentacoordinate tin complexes. Of the complexes selected to be screened against five tumour cell lines, some exhibited significant in vitro activity.  相似文献   

7.
The zinc(II), copper(II), nickel(II), and cobalt(II) complexes of Schiff bases, obtained by the condensation of cefixime with furyl-2-carboxaldehyde, thiophene-2-carboxaldehyde, salicylaldehyde, pyrrol-2-carboxaldehyde, and 3-hydroxynaphthalene-2-carboxaldehyde, were synthesized and characterized by their elemental analyses, molar conductances, magnetic moments, IR, and electronic spectral measurements. Analytical data and electrical conductivity measurements indicated the formation of M?:?L (1?:?2) complexes, [M(L)2(H2O)2] or [M(L)2(H2O)2]Cl2 [where M?=?Zn(II), Cu(II), Ni(II), and Co(II)] in which ligands are bidentate via azomethine-N and deprotonated-O of salicyl and naphthyl, furanyl-O, thienyl-S, and deprotonated pyrrolyl-N. The magnetic moments and electronic spectral data suggest octahedral complexes. The synthesized ligands, along with their metal complexes, were screened for their antibacterial activity against different bacterial strains. The studies show the metal complexes to be more active against one or more species as compared to the uncomplexed ligands.  相似文献   

8.
Transition metal (NiII, CoII, and CuII) complexes with 1,2-bis[2-(3-pyridylmethylideneamino)phenylthio]ethane (1) and 1,2-bis[2-(4-pyridylmethylideneamino)phenylthio]ethane (2) were synthesized for the first time by slow diffusion of solutions of compounds 1 or 2 in CH2Cl2 into solutions of MX2 · nH2O (M = Ni, Co, or Cu; X = Cl or NO3; n = 2 or 6) in ethanol. The reactions with CoII and CuII chlorides afford complexes of composition M(L)Cl2 (L = 1 or 2). The reactions of compound 1 with NiII salts produce complexes with 1,2-bis(2-aminophenylthio)ethane. The molecular structure of dinitrato[1,2-bis(2-aminophenylthio)ethane]nickel(ii) was confirmed by X-ray diffraction. The ligands and the complexes were investigated by cyclic voltammetry and rotating disk electrode voltammetry. The initial reduction of the complexes proceeds at the metal atom. The oxidation of the chlorine-containing complexes proceeds at the coordinated chloride anion. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 350–355, February, 2008.  相似文献   

9.
Summary 3-(2-Furyl) 2-propene aldoxime (FAOH) and 3-(5-methyl 2-furyl) 2-propene aldoxime (M5FAOH) react, in stoichiometric amounts, with 3d divalent metal halides MX2(M=Mn, Co, Ni, Cu and Zh; X=Cl or Br) to givetrans-octahedral complexes, except the ZnCl2 derivative with FAOH which is tetrahedral. These ligands are bidentate in [ML2X2] species (L=FAOH or M5FAOH) through the cyclic oxygen atom and the oxime nitrogen, and are monodentate for [ML4X2] complexes and [ZnCl2(FAOH)2] through the N-oxime atom. The structures were established by analytical and spectroscopic data.  相似文献   

10.
Yang  Jin  Ma  Jian-Fang  Wu  Dong-Mei  Guo  Li-Ping  Liu  Jing-Fu 《Transition Metal Chemistry》2003,28(7):788-793
Three new compounds, namely [Mn(phen)2(L)2] · EtOH (1), [Zn(phen)2(H2O)2]2L · 6H2O (2) and [Cd(phen)2(H2O)2]2L · 6H2O (3), where HL = 4-methylbenzenesulfonic acid and phen = o-phenanthroline, have been synthesized, and their crystal structures determined by X-ray diffraction. In the complexes the metal atoms have two different coordination environments. Complex (1) consists of neutral molecules, [Mn(phen)2(L)2], in which MnII is six-coordinated by four nitrogen atoms from two o-phenanthroline molecules and two oxygen atoms from two sulfonate ions. Complexes (2) and (3) are isomorphous, each consisting of cationic species [M(phen)2(H2O)2]2+ [M = Zn (2), Cd (3)], in which MII is six-coordinated by four nitrogen atoms from two o-phenanthroline molecules and two water molecules. The electrochemical behavior and FT-IR of these compounds were also studied in detail.  相似文献   

11.
《Polyhedron》1999,18(6):863-869
Electrochemical oxidation of metal anodes (cobalt, copper and nickel) in acetonitrile solutions of 2-(2-hydroxyphenyliminomethyl)-1-(4-methyl-phenylsulfonamido)benzene (H2L) gave [CoL], [CuL] and [NiL] complexes. When 1,10-phenanthroline (phen) or 2,2′-bipyridine (bipy) was added to the electrolytic cell, the mixed complexes [MLL′] (M=Co, Cu, L′=bipy or M=Ni, L′=phen) were obtained. A binuclear compound of composition [Ni2L2(MeOH)4] (1) was synthesized by reaction of the ligand H2L and nickel(II) acetate in methanol. X-ray structure determination showed the compound to be binuclear, with each nickel atom coordinated to two nitrogen and two bridging phenol oxygen atoms of two dianionic ligands and two methanol molecules, in an octahedral environment. The crystal structure of [CuLbipy] (2) was determined by X-ray diffraction; with the copper atom in a distorted bipyramidal environment defined by the two bipyridine nitrogen atoms and by the phenolic oxygen and the nitrogen atoms of the dianionic ligand. The electronic and vibrational spectral data of the complexes are discussed and related to the structure.  相似文献   

12.
An interesting series of cobalt(II) complexes of the new ligands: 4[N-(benzalidene)amino]antipyrinethiosemicarbazone (BAAPTS), 4[N-(2′-hydroxy-benzalidene)amino]antipyrinethiosemicarbazone (HBAAPTS) and 4[N-(2′-hydroxy-1′-naphthalidene)amino]antipyrinethiosemicarbazone (HNAAPTS) were synthesized by reaction with Co(II) salts in ethanol. The general stoichiometry of the complexes was found to be [CoX2(H2O)(L)] and [Co(L)2](ClO4)2, where X = Cl, NO3, NCS or CH3COO and L = BAAPTS, HBAAPTS or HNAAPTS. The complexes were characterized by elemental analysis, molar conductivity measurement, molecular weight determination, magnetic moments at room temperature, infrared and electronic spectra. All the thiosemicarbazones behave as neutral tridentate (N, N, S) donor ligands. The conductivity measurements in PhNO2 solution indicated that the chloro, nitrato, thiocyanato and acetate complexes are essentially non-electrolytes, while the perchlorate complexes are 1:2 electrolytes. Thermogravimetric studies were performed for some representative complexes and the decomposition mechanism proposed. Antibacterial and antifungal properties of the ligands and their cobalt(II) complexes have also been examined and it has been observed that the complexes are more potent bactericides than the ligand.  相似文献   

13.
The complexes [K(H2O)2LnL2] (Ln = La or Nd; L = 1,2‐benzenedisulfonate) and [K(H2O)Yb(H2O)4L2] were initially isolated fortuitously from attempts to prepare the corresponding Ln2L3 complexes from Ln2O3 and H2L in water. Indeed the bulk products from these reactions have the composition Ln2L3. Subsequently, deliberate syntheses by reacting equimolar amounts of Ln2L3 with K2L in water gave the complexes in good yield. X‐ray crystal structures of [K(H2O)2LnL2] (Ln = La or Nd) showed the complexes to be isostructural with a two dimensional polymeric network structure in which LnL2 units are linked into chains crosslinked by potassium ions. Each Ln is nine coordinate with solely sulfonate oxygen donor atoms. Between adjacent lanthanoid ions there are three different types of sulfonate bridges and two examples of each. Most noteworthy is highly unsymmetrical bridging through μ‐η2‐sulfonate oxygen atoms. Consequently, one Ln–O bond is ca. 0.5 Å longer than the other eight. Potassium is nine‐coordinate with seven sulfonate oxygen atoms and two aqua ligands, and surprisingly <K–O(sulfonate)> is much longer than <K–O(H2O)>. Pairs of potassium ions are linked by two μ‐η2‐sulfonate oxygen atoms, which are unsymmetrically bridging. The structure of [K(H2O)Yb(H2O)4L2] comprises discrete tetranuclear units containing two independent ytterbium ions, each coordinated by four water molecules and two chelating (via seven membered rings) disulfonate ligands, and two potassium ions, each coordinated by six sulfonate oxygen atoms and a water molecule. For each potassium, four of the coordinated sulfonate oxygen atoms are from sulfonate ligands bonded to one ytterbium atom and two from sulfonate ligands attached to the other ytterbium atom. In contrast to the Nd and La complexes, <K–O(sulfonate)> is shorter than <K–O(H2O)>.  相似文献   

14.
Summary Bivalent metal complexes ofp-chloro-,p-methyl- andp-methoxybenzoylhydrazone oximes (H2BMCB, H2BMMB or H2BMTB=H2L), [M(H2L)Cl2]. nH2O (M=ZnII, CdII or HgII, n=0 or 1; [M(H2L)Cl2] (M=ZnII or CdII); [M(HL)2(H2O)n]. YH2O (M=CoII, CuII, ZnII or UVIO2, n=0–2); [Ni(H2BMCB)(H2O)3]Cl2, [Ni(BMMB)(H2O)]2 and [Ni(BMTB)(H2O)]2, were synthesized by conventional physical and chemical measurements. I.r. spectra show that the ligands are bidentate or tridentate. Spectral, magnetic and molecular weight measurements suggest that cobalt(II) and nickel(II) have monomeric octahedral geometry when derived from H2BMCB, a dimeric square planar geometry for nickel(II) and monomeric square planar geometry for cobalt(II) for those isolated from H2BMMB or H2BMTB. Also, a monomeric distorted octahedral structure is proposed for copper(II) complexes derived from the ligands under investigation.  相似文献   

15.
The reaction of copper(II) salts with (E)-N-(2-hydroxy-1,2-di(pyridin-2-yl)ethylidene)aroyl hydrazide (H2L1, H2L2, H3L3) or (E)-N-(2-hydroxy-1,2-di(pyridin-2-yl)ethylidene) isonicotinohydrazide (H2L4) afforded the complexes [(L)Cu(H2O)3], [(H2L)Cu(OAc)(H2O)], [(HL)Cu(OAc)] n , [(H2L)Cu(H2O)](ClO4)2 and [(H2L)Cu(OAc)(H2O)], where n = 1 or 2 and L is the dinegative ion of the ligands. The ligands and their complexes are characterized by elemental analyses, spectral (IR, NMR, electronic, and ESR) and magnetic studies. The FT-IR indicates that the ligands are neutral or anionic polydentate. The number of the coordinating centers depends on the nature of the metal used and the reaction conditions. The room temperature magnetic moment values, electronic spectra and ESR data indicate square planar, trigonal bipyramidal, square pyramidal, and distorted octahedral ligand fields around copper(II). Thermal decomposition of the complexes was monitored by TG and DTG under N2 and the thermal decomposition mechanisms are given. The compounds were screened for their antimicrobial activities on some Gram-positive and Gram-negative bacterial species. The free ligands are inactive against all studied bacteria. The complexes have variable activity with the most active [(H2L)Cu(H2O)](ClO4)2, where H2L is H2L1 or H2L2. The minimum inhibition concentrations for these two complexes were determined. These biological activity results are related to the structures of the compounds.  相似文献   

16.
The fast atom bombardment mass spectra of a series of neutral methanide and ionic carbene platinum(II) complexes of formula dPePtL2 and [dPePt(LH)2](BF4)2 (dPe = (C6H5)2PCH2CH2P(C6H5)2; L = ? C(OCH3)-NCH3, ? C(OCH3) ? NC6H11, ? C(OCH3) ? NC6H4p ? CH3), respectively are reported. Glycerol, 3-mercapto-1,2-propanediol, bis (2-hydroxyethyl)sulphide, 3-nitrobenzyl alcohol, and 2,4-di-tert-pentylphenol have been used as matrices. Neutral and ionic derivatives containing the same ligand behave similarly and give the same quasi-molecular [dPePtL(L + H)]+ ion by different primary processes. Stepwise breakdown of the ligands L with retention or further loss of atoms or molecules of hydrogen is observed for all these complexes, followed by ejection of radicals from the dPe ligand. Elimination of CH3OH from [dPePtL(L + H)]+ also occurs. The highest ionic yields of both neutral methanide and ionic carbene complexes are observed in 3-mercapto-1,2-propanediol, in bis(2-hydroxyethyl)sulphide, and in 3-nitrobenzyl alcohol with respect to glycerol. The [dPePt(LH)2]2+ doubly charged ions are present in the spectra obtained with 3-nitrobenzyl alcohol and are rather strong when L is ? C(OCH3) ? NCH3 and ? C(OCH3) ? NC6H4p ? CH3. Substitution of ligands L with a molecule or with a fragment of a sulphur containing matrix takes place very seldom with this series of complexes.  相似文献   

17.
bis(alkoxycarbonyl) complexes of platinum of the type [Pt(COOR)2L] [L = 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), l,4-bis(diphenylphosphino)butane (dppb), 1,1'-bis(diphenylphosphino)ferrocene (dppf) or 1,2-bis-(diphenylphosphino)benzene (dpb); R = CH3, C6H5 or C2H5] were obtained by reaction of [PtCl2L] with carbon monoxide and alkoxides. Palladium and nickel complexes gave only carbonyl complexes of the type [M(CO)L] or [M(CO)2L]. The new complexes were characterized by chemical and spectroscopic means. The X-ray structure of [Pt(COOCH3)2(dppf] · CH3OH is also reported. The reactivity of some alkoxycarbonyl complexes was also investigated.  相似文献   

18.
Treatment of [BzPh3P][AuCl2] with [Hg(x-C6H4NO2)2] (x = o, m, or p) gives anionic gold(I) complexes of the type [BzPh3P][Au(R)Cl](R = o-, m- or p-C6H4NO2, Bz = C6H5CH2). The chloro ligand in [Au(o-C6H4NO2)Cl]? can be replaced by bromo or iodo ligands by use of NaBr or NaI. The anions [Au(R)Cl]? react with neutral monodentate ligands, L, to give neutral mononuclear complexes [Au(R)L] (R = o-C6H4NO2, L = PPh3, AsPh3; R = m-C6H4NO2, L = PPh3) and with 1,2-bis(diphenylphosphino)ethane (dpe) to give [Au2(R)2(dpe)] (R = o-C6H4NO2). The corresponding [Au(p-C6H4NO2)Cl]? reacts with PPh3 or AsPh3 to give mixtures containing [AuClL]. The anionic ortho-nitrophenylgold(I) complex is much more stable than its meta- or para-nitrophenyl isomers. These are thought to be the first reports of nitrophenylgold(I) complexes.  相似文献   

19.
The compounds of 2-(5-chloro/nitro-1H-benzimidazol-2-yl)-4-bromo/nitrophenols (HLX : X = 1–4) and their copper(II) nitrate and iron(III) nitrate complexes have been synthesized and characterized. The structures of the complexes were confirmed on the basis of elemental analysis, thermal gravimetric analysis, molar conductivity and magnetic moment measurements, FT-IR, mass, and UV-Vis spectroscopy techniques. The complexes show high-thermal stability with >350°C m.p. In all complexes, the ligands are bidentate via one imine nitrogen and a phenolate oxygen. Cu(II) complexes having 1 : 2 M : L ratio are classified as non-electrolytes, whereas 1 : 1 M : L ratio is observed in Fe(III) complexes except [Fe(L3)2(H2O)2](NO3) ? 3H2O. The antimicrobial activities of the ligands and the complexes were evaluated using the disc diffusion method in DMSO as well as minimum inhibitory concentration dilution method against Staphylococcus aureus, Staphylococcus epidermidis, Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, and Proteus mirabilis. Antifungal activities were reported for Candida albicans. The complexes [Fe(L3)2(H2O)2](NO3) ? 3H2O and [Cu(L3)2] ? 2H2O are more effective against S. epidermidis than ciprofloxacin.  相似文献   

20.
Reaction of [MoO2(Acac)2] (Acac = acetylacetonate) with two similar hydrazone ligands in methanol yielded two mononuclear molybdenum(VI) oxocomplexes with general formula [MoO2(L)(CH3OH)], where L = L1 = (4-nitrophenoxy)acetic acid [1-(3-ethoxy-2-hydroxyphenyl)methylidene]hydrazide (H2L1) and L = L2 = (4-nitrophenoxy)acetic acid [1-(5-bromo-2-hydroxyphenyl)methylidene]hydrazide (H2L2). Crystal and molecular structures of the complexes were determined by single crystal X-ray diffraction method. All investigated compounds were further characterized by elemental analysis and FT-IR spectra. Single crystal X-ray structural studies indicate that the hydrazone ligands coordinate to the MoO2 cores through enolate oxygen, phenolate oxygen, and azomethine nitrogen. The Mo atoms in both complexes are in octahedral coordination.  相似文献   

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