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1.
A new vic-dioxime, N-{4-[[(2-hydroxyphenyl)methylene]hydrazinecarbonyl]phenyl}aminoglyoxime (H3L), was prepared by the reaction of anti-chloroglyoxime with salicylaldehyde 4-aminobenzoylhydrazone. The reaction of H3L with Cu(II) salts and an appropriate simple ligand gave only homotrinuclear complexes [Cu3(HL)2X2], whereas the reaction of H3L with Ni(II) salts gave mono-and homotrinuclear complexes [Ni(H2L)2 and Ni3(HL)2X2]. Also, heterotrinuclear complexes of H3L were prepared by the reaction of Ni(H2L)2 with Cu(II) salt and an appropriate simple ligand, [NiCu2(HL)2X2], X = Cl, NO 3 , SCN, CN, and N 3 . The new vic-dioxime and its complexes were identified by elemental analyses, IR, 1H NMR, UV-VIS, magnetic susceptibility, and mass spectral data. The elemental analyses and spectral data indicated that the hydrazone side of H3L acted as monobasic tridentate and the fourth position was occupied by simple ligands, such as Cl, NO 3 , SCN, CN, and N 3 . The text was submitted by the author in English.  相似文献   

2.
Thermal decomposition of binary complexes [M(NH3) k ] x [M′L n ] y (M = Ni, Co; M′ = Fe, Cr, Cu; L = CN, SCN, C2O42−) in a hydrogen atmosphere showed conversion of coordinated CN groups into ammonia and hydrocarbons; SCN into ammonia, hydrogen sulfide, and hydrocarbons; and C2O42− into hydrocarbons and CO2. In all cases, methane prevails in the resulting hydrocarbons; ethylene is the second in relative yield, which however strongly depends on the temperature and combination of the central ions of double complex salts. The yield of ethylene is especially high from the reduction of Co-Fe complexes at 350°C, Co4-Fe3 complexes at 500°C, Ni3-Fe2 and Ni3-Cr2 complexes at 350°C. The observed conversions of coordinated groups can be interpreted as arising from the catalytic effect caused by the reduced forms of the central atoms in the binary complexes to the interaction of ligands with hydrogen.  相似文献   

3.
A new vicinal dioxime ligand with two crown-ether groups, 1,2-bis[(monoaza[15]crown-5)-N-Yl]-glyoxime(LH2), has been prepared from cyanogen di-N-oxide and monoaza[15]crown-5. Ni(II), Pd(II), and Pt(IV) complexes of LH2 with or without alkali-metal ions bound to macrocyclic groups have been isolated. The high affinity of [Pd(LH)2] and [Ni(LH)2] for the K+ ion is observed in solvent extraction experiments. A single-crystal X-ray structure confirms the postulated geometry of [Pd(LH)2]- The Pd-atom of the centro-symmetric molecule has square-planar PdN4 coordination where Pd–N distances range from 1.978(3) to 1.970(3) Å. The N–Pd–N intraligand angle is 79.9(1)°.  相似文献   

4.
N,N′-bis(salicylidene)-1,3-propanediamine (LH2), N,N′-bis(salicylidene)-2,2′-dimethyl-1,3-propanediamine (LDMH2), N,N′-bis(salicylidene)-2-hydroxy-1,3-propanediamine (LOH3), N,N′-bis(2-hydroxyacetophenylidene)-1,3-propanediamine (LACH2) and N,N′-bis(2-hydroxyacetophenone)-2,2′-dimethyl-1,3-propanediamine (LACDMH2) were synthesized and reduced to their phenol-amine form in alcoholic media using NaBH4 (LHH2, LDMHH2, LOHHH2, LACHH2 and LACDMHH2). Heterodinuclear complexes were synthesized using Ni(II), Zn(II) and Cd(II) salts, according to the template method in DMF media. The complex structures were analyzed using elemental analysis, IR spectroscopy, and thermogravimetry. Suitable crystals of only one complex were obtained and its structure determined using X-ray diffraction, NiLACH·CdBr2·DMF2, space group orthorhombic, Pbca, a=20.249, b=14.881, c=20.565 ? and Z=8. The heterodinuclear complexes were seen to be of [Ni·ligand·MX2·DMF2] structure (ligand=LH2−, LDMH2−, LOHH2−, LACH2−, LACDMH2−, M=ZnII, CdII, X=Br, I). Thermogravimetric analysis showed irreversible bond breakage of the coordinatively bonded DMF molecules followed by decomposition at this temperature.  相似文献   

5.
CoII, NiII, CuII, ZnII and CdII complexes of N,N-bis(2-{[(2-methyl-2-phenyl-1,3-dioxolan-4-yl)methyl]amino}butyl)N′,N′-dihydroxyethanediimidamide (LH2) were synthesized and characterized by elemental analyses, IR, 1H- and 13C-NMR spectra, electronic spectra, magnetic susceptibility measurements, conductivity measurements and thermogravimetric analyses (TGA). The CoII, NiII and CuII complexes of LH2 were synthesized with 1?:?2 metal ligand stoichiometry. ZnII and CdII complexes with LH2 have a metal ligand ratio of 1?:?1. The reaction of LH2 with CoII, NiII, CuII, ZnII and CdII chloride give complexes Ni(LH)2, Cu(LH)2, Zn(LH2)(Cl)2, Cd(LH2)(Cl)2, respectively.  相似文献   

6.
A new vic-dioxime ligand, N,N′-bis(aminopyreneglyoxime) (LH2), and its copper(II), nickel(II) and cobalt(II) metal complexes were synthesized and characterized by elemental analyses, IR, UVVIS and 1H and 13C NMR spectra (for the ligand). Mononuclear complexes were synthesized by a reaction of ligand (LH2) and salts of Co(II), Ni(II), and Cu(II) in ethanol. The complexes have the metal-ligand ratio of 1: 2 and metals are coordinated by N,N′ atoms of vicinal dioximes. The ligand acts in a polydentate fashion bending through nitrogen atoms in the presence of a base, as do most vic-dioximes. Detection of a H-bonding in the Co(II), Ni(II), and Cu(II) complexes by IR revealed the square-planar MN4 coordination of mononuclear complexes. Fluorescent properties of the ligand and its complexes arise from pyrene units conjugated with a vic-dioxime moiety. Fluorescence emission spectra of the ligand showed a drastic decrease in its fluorescence intensity upon metal binding. The electrochemical properties of the complexes were studied by the cyclic voltammetry technique. The nickel complex displayed an irreversible oxidation process while the copper complex exhibited a quasi-reversible oxidation and reduction processes based on the copper Cu(II)/Cu(III) and Cu(II)/Cu(I) couples, respectively.  相似文献   

7.
A new vicinal dioxime ligand containing azo and thione chromophores, namely 1,3-bis[4-(phenyldiazenyl)phenyl]-2-thiooxaimidazoline-4,5-dione dioxime (bppH2), was synthesized by the reaction of cyanogen di-N-oxide with N,N′-bis(4-phenylazophenyl) thiourea in dichloromethane solution at −10 °C. Mononuclear complexes of bppH2 with nickel(II), cobalt(II), and copper(II) were synthesized. The complexes, [Ni(bppH)2], [Cu(bppH)2], and [Co(bppH)2] were characterized by several techniques using elemental analyses, conductivity measurements, FT-IR, and electronic spectral studies. The data suggest that the ligand coordinates through the N,N atoms, as do most vic-dioximes. The molar conductivities in DMF solution indicate nonelectrolytic nature for the complexes. Antimicrobial activities of the ligand and its metal complexes were estimated for five bacteria, namely Klebsiella pneumoniae, Micrococcus luteus, Mycobacterium smegmatis, Enterobacter cloaca and Bacillus megaterium and three fungi, namely Candida albicans, Kluyveromyces marxianus, and Rhodotorula rubra.  相似文献   

8.
Parent and mixed ligand complexes of cobalt and copper with antipyrine derivatives of 1,2-ethanediamine or piperazine and with 2-aminobenzothiazole (TAB) were synthesized and their thermal behaviour was investigated. The complexes contain N,N′-bis(4-antipyrylmethyl)-piperazine (BAMP) or N,N′-tetra(4-antipyrylmethyl)-1,2-diaminoethane (TAMEN) or/and TAB as ligand, and Cl, ClO4 or SCN. The complexes decompose with the evolution of heat. The decomposition route depends on the presence of ClO4 . If the ClO4 is not coordinated, it oxidizes the TAB and BAMP or TAMEN and the decomposition is explosive. This revised version was published online in August 2006 with corrections to the Cover Date.  相似文献   

9.
Copper(II)-pyrrolidine dithiocarbamate (PDTC) complexes having the general formula, [Cu(PDTC)2], [Cu(PDTC)X2] (where X = Cl, I, CN, SCN) and [Cu(PDTC)(en)]+ (en = ethylenediamine) have been prepared and characterized by IR spectroscopy and by thermogravimetric analysis (TGA and DTA). The IR data suggests that coordination of pyrrolidine dithiocarbamate (PDTC) takes place through the two sulphur atoms in a symmetrical bidentate fashion. The results of thermal analysis are consistent with the proposed composition of the complexes.  相似文献   

10.
The reactions of the oxalate complexes [M3Q7(C2O4)3]2− (M = Mo or W; Q = S or Se) with MnII, CoII, NiII, and CuII aqua and ethylenediamine complexes in aqueous and aqueous ethanolic solutions were studied. The previously unknown heterometallic complexes [Mo3Se7(C2O4)3Ni(H2O)5]·3.5H2O (1) and K3{[Cu(en)2H2O]([Mo3S7(ox)3]2Br)}·5.5H2O (2) were synthesized. In these complexes, the oxalate clusters serve as monodentate ligands. The K(H2en)2[W3S7(C2O4)3]2Br·4H2O salt (3) was isolated from solutions containing CoII, NiII, or CuII aqua complexes and ethylenediamine. The reaction of [Mo3Se7(C2O4)3]2− with HBr produced the bromide complex [Mo3Se7Br6]2−, which was isolated as (Bu4N)2[Mo3Se7Br6] (4). Complexes 1–3 were characterized by X-ray diffraction, IR spectra, and elemental analysis. The formation of 4 was detected by electrospray mass spectrometry. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1645–1649, September, 2007.  相似文献   

11.
A new vic-dioxime bearing coumarin functionality, N1,N2-Dihydroxy-N 1,N 2-bis(4-methyl-2-oxo-2H-chromen-7-yl)oxalimidamid (LH2), N,N-bis-[4-methylcoumarinyl]-diamino glyoxime (LH2), and its mono- and dinuclear complexes {copperII, cobaltII, nickelII and uranylII} have been reported. The fluorescence excitation and emission spectra of LH2 and its complexes with metal ions were examined. It was observed that fluorescence and excitation emission intensity of LH2 was quenched depending on complex formation with metal ions. The characterizations of all newly synthesized compounds were made by elemental analysis, 1H-n.m.r, i.r., u.v.–vis., and l.c-m.s./m.s. data. Electrochemical behaviour of the ligand involving oxime and coumarine moieties, and its complexes with NiII, CuII, CoII and UO 2 II were investigated by cyclic voltammetry. The comparison of the electrochemical behaviour of the ligand with its complexes enabled us to identify metal-, oxime- and coumarine-based signals.  相似文献   

12.
New bis-benzimidazole based diamide ligands N, N′-bis(2-methyl benzimidazolyl)-benzene-1,3-dicarboxamide [GBBA] and N-Octyl-N, N′-bis(2-methyl benzimidazolyl)-benzene- 1,3-dicarboxamide [O-GBBA] have been synthesized and utilized to prepare Cu(II) complexes of general composition [Cu(GBBA)X 2] · nH2O and [Cu(O-GBBA)X2] · n H2O, where X is an exogenous anionic ligand (X = Cl, NO3, SCN). The oxidation of electron deficient olefins has been investigated using [Cu(O-GBBA)X2] · nH2O as catalyst and TBHP as an alternate source of oxygen. The respective ketonic products have been isolated and characterized by 1H-NMR. The complex [Cu(GBBA)(NO3)2] · 4H2O has been characterized structurally. It crystallizes in a monoclinic space group C2/c. Low temperature EPR spectra have been obtained for the complexes that shows gII > gI > 2.0024, indicating a tetragonal geometry in the solution state. The complexes display a quasi reversible redox wave due to the Cu(II)/Cu(I) reduction process. The E1/2 values shift anodically as NO3 < SCN < Cl.  相似文献   

13.
The kinetics of nucleophilic substitution of pyridine in bis-cationic [Pt(L)(py)]2+ complexes (L=SNS, NNN, NSN) [SNS=bis(methylthiomethyl)pyridine, NNN=bis(2-pyridylmethyl)amine, NSN=bis(2-pyridylmethyl)sulphide] by a series of nucleophiles (Cl, Br, I, N3, (C2H5)2S, NH3, thiourea (tu), NO2, C5H10NH, SeCN, SCN, CN when L=SNS; Cl, Br, I, N3, (C2H5)2S, SCN, NH3, NO2 when L=NNN; Br, N3, NO2, NH3, C5H10NH when L=NSN) have been measured in MeOH at 25 °C, μ =0.1 mol dm−3 (LiClO4 or LiCF3SO3). The logarithms of the second-order rate constants calculated at μ=0, log k° 2, do not follow the dependence upon the n° Pt scale. In particular, the reactivity of the biphilic reagents tu, SeCN, SCN and, to a lesser extent, NO 2, towards these doubly charged substrates is largely lower than expected on the basis of the n° Ptscale. There are good linear relationships between logk° 2 for the bis-cationic substrate [Pt(SNS)(py)]2+, chosen as the standard, and log k° 2 for the same reactions with [Pt(NNN)(py)]2+, [Pt(NSN)(py)]2+ and other double charged complexes previously studied. A new wide nucleophilicity scale based on [Pt(SNS)(py)]2+, that is appropriate to all the bis-cationic substrates, is here proposed  相似文献   

14.
The reaction of [M(L)]Cl2 · 2H2O (M = Ni2+ and Cu2+, L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane) with 1,1-cyclobutanedicarboxylic acid (H2-cbdc) generates 1D and 2D hydrogen-bonded infinite chains [Ni(L)(H-cbdc)2] (1) and [Cu(L)(H-cbdc)2] (2). (H-cbdc = cyclobutane-1-carboxylic acid-1-carboxylate). These complexes have been characterized by X-ray crystallography, spectroscopy, and cyclic voltammetry. The crystal structure of 1 shows a distorted octahedral coordination geometry around the nickel(II) ion, with four secondary amines and two oxygen atoms of the H-cbdc ligand at the trans position. In 2, the coordination environment around the central copper(II) ion shows a Jahn–Teller distorted octahedron with four Cu–N bonds and two long Cu–O distances. The cyclic voltammogram of the complexes undergoes two one-electron waves corresponding to MII/MIII and MII/MI processes. The electronic spectra and electrochemical behavior of the complexes are significantly affected by the nature of the axial H-cbdc ligand.  相似文献   

15.
The design, synthesis and coordination of a novel multisite vic-dioxime compound, LH2, containing flexible pyridine substituents and aminophenylsulfanyl moieties on the periphery, facilitating solubility in water as pyridinium hydrochloride salt are described. LH2 was prepared by the reaction between 2-(2-pyridylethylamino)-benzenethiol and (E,E)-dichloroglydioxime. Mononuclear [(E,E)M] (M=NiII, CuII, CoII, FeII and MnII) and dinuclear uranyl (UO2 II) complexes of LH2 were isolated and characterized with metal:ligand ratios of 1:2 and 2:2, respectively. The reaction of Na2PdCl4·3H2O and AgNO3 in DMF with the mononuclear complex, (LH)2Ni, resulted in the formation of the heterotrinuclear complexes [Pd2Ni(LH)2]Cl4 and [Ag2Ni(LH)2](NO3)2. The complexes were characterized by elemental analysis, 1H-n.m.r., u.v.--vis. spectroscopy, i.r., and MS (LSIMS). The redox properties of the complexes were studied by cyclic voltammetry.  相似文献   

16.
    
The mixed valence Mn(III, IV) complexes, [Mn2O2L4]X3 with L=2,2-bipyridine or 1,10-phenanthroline and X=ClO 4 or PF 6 undergo partial ligand displacement reactions giving rise to the new compounds [Mn2O2L3A2]X3 with A=N, N-dimethylformamide or pyridine. The substitution is believed to take place at the labiled 4, Mn(III) centre. The substituted complexes have more deeply trapped valencies based on their electronic spectral characteristics. The EPR spectra are found to be essentially unaffected by ligand substitutions. Computer simulations of frozen solutions as well as polycrystalline spectra of the PF 6 salts showing hyperfine splittings are presented. All the complexes evolve oxygen from water when present as a solid phase in contact with an aqueous solution containing Ce4+ions. The oxygen-evolving solution is found to contain MnO 4 ions.  相似文献   

17.
A new series of dioxouranium(VI) complexes of a potential ONNO tetradentate donor 2-aminobenzoylhydrazone of butane-2,3-dione (L1H2) have been synthesized. At pH 2·5–4·0, the donor (L1H2) reacts in the keto form and complexes of the type [UO2(L1H2)(X)2] (X=Cl, Br, NO 3 , NCS, ClO 4 , CH3COO, 1/2SO 4 2− ) are obtained. At higher pH (6·5–7), the complex of the enol form having the formula [UO2(L1)(H2O)] has been isolated. On reaction with a monodentate lewis base (B), both types of complexes yield adducts of the type [UO2(L1)(B)]. All these complexes have been characterised adequately by elemental analyses and other standard physicochemical techniques. Location of the bonding sites of the donor molecule around the uranyl ion, status of the uranium-oxygen bond and the probable structure of the complexes have also been discussed.  相似文献   

18.
Synthesis and deprotonation reactions of half‐sandwich iridium complexes bearing a vicinal dioxime ligand were studied. Treatment of [{Cp*IrCl(μ‐Cl)}2] (Cp*=η5‐C5Me5) with dimethylglyoxime (LH2) at an Ir:LH2 ratio of 1:1 afforded the cationic dioxime iridium complex [Cp*IrCl(LH2)]Cl ( 1 ). The chlorido complex 1 undergoes stepwise and reversible deprotonation with potassium carbonate to give the oxime–oximato complex [Cp*IrCl(LH)] ( 2 ) and the anionic dioximato(2?) complex K[Cp*IrCl(L)] ( 3 ) sequentially. Meanwhile, twofold deprotonation of the sulfato complex [Cp*Ir(SO4)(LH2)] ( 4 ) resulted in the formation of the oximato‐bridged dinuclear complex [{Cp*Ir(μ‐L)}2] ( 5 ). X‐ray analyses disclosed their supramolecular structures with one‐dimensional infinite chain ( 1 and 2 ), hexagonal open channels ( 3 ), and a tetrameric rhomboid ( 4 ) featuring multiple intermolecular hydrogen bonds and electrostatic interactions.  相似文献   

19.
Summary The new complexes K2[ML2]·2H2O (M=Ni, Cu), K2[PdL2]·H2O, K2[CuL2(H2O)2]·H2O, [Ni(LH2)Cl2]x ·xH2O and [Ni(LH2)Br2]x·1,5xH2O, where LH2= oxalyldihydrazide, have been prepared. Emphasis has been put on determining the conditions for the synthesis of both deprotonated and non-deprotonated NiII complexes. They were characterized by analyses, conductivity measurements, thermogravimetry, magnetic susceptibility and spectroscopic methods like i.r. and far-i.r., diffuse reflectance u.v. vis, and e.s.r. Monomeric square planar and distorted octahedral structures were found for the deprotonated complexes in the solid state while the non-deprotonated NiII complexes appeared to be pseudo-tetrahedral polymers. The doubly deprotonated L2-ion exhibits a bidentate N(amide), N(amide)-coordination, while the neutral LH2 molecule behaves as a N(amino), N(amino)-bidentate ligand forming polymeric structures. Vibrational analysis of the complexes was carried out, using hydrogen and metal isotopic substitution.  相似文献   

20.
A novel vic-dioxime ligand with a thiourea moiety, (4E,5E)-1,3-bis{4-[(4-bromophenylamino)methylene]phenyl}-2-thiooxaimidazoline-4,5-dione dioxime (4) (bmdH2) has been synthesized from N,N′-bis{4-[(4-bromophenylamino)methylene]phenyl}thiourea and (E,E)-dichloroglyoxime. The bmdH2 ligand (4) forms transition metal complexes [M(bmdH)2] with a metal?:?ligand ratio of 1?:?2 with M?=?Ni(II), Co(II), and Cu(II). The mononuclear Ni(II), Co(II) and Cu(II) complexes, [Ni(bmdH)2] (5), [Co(bmdH)2] (6) and [Cu(bmdH)2] (7) have the metal ions coordinated through the two N,N atoms, as do most vic-dioximes. Elemental analyses, molar conductivity, magnetic susceptibility, IR, 1H NMR spectra, and UV-Visible spectroscopy were used to elucidate the structures of the ligand and its complexes. Conductivity measurements have shown that the mononuclear complexes are non-electrolytes. In addition, the ligands and metal complexes were screened for antibacterial and antifungal activities by agar well diffusion techniques using DMF as solvent.  相似文献   

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