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1.
《Polyhedron》1999,18(21):2787-2793
New binuclear complexes of the type [(Ni(Medpt)NO3)2ox] (1) (Medpt=3,3′-diamino-N-methyl-dipropylamine, H2ox=oxalic acid), [(Ni(dach)2)2ox]NO3·2H2O (2) (dach=trans-1,2-diaminocyclohexane), [(Cu(Medpt))2ox]X2·yH2O (X=NO3, y=2 2/3 (3); X=ClO4, y=0 (4)) and [(Zn(dach)2)2ox](ClO4)2·2H2O (5) have been prepared and characterized by IR and UV–Vis spectroscopies. Spectroscopic data are consistent with oxalate-bridged structures between six-coordinated (N3O3 or N4O2) Ni(II) (compounds 1 or 2), five-coordinated (N3O2) Cu(II) (compounds 3 and 4) or six-coordinated (N4O2) Zn(II) (compound 5). The crystal structure of [(Cu(Medpt))2ox](NO3)2·2 2/3 H2O (3) has been determined by single-crystal X-ray analysis. The structure of (3) consists of centrosymmetric binuclear cations [(Medpt)Cu(ox)Cu(Medpt)]2+, nitrate anions and water molecules of crystallization. The copper atom is five-coordinated by two oxalate–oxygen and three Medpt–nitrogen atoms, in a hybrid arrangement between trigonal–bipyramidal and square–pyramidal. The temperature dependence of magnetic susceptibility (1.8–300 K) was measured for compounds 14. Magnetochemical measurements show that Ni(II) complexes are antiferromagnetically coupled, J=−29.4 (1) and −32.7 cm−1 (2) (H=−JS1S2) while the Cu(II) complexes present a very weak coupling, J=−2.6 (3) and +1.9 cm−1 (4), being antiferro- and ferromagnetic in nature.  相似文献   

2.
The new complexes M(LH)2 (M = Pd,Pt), ML(M = Pd,Cu) and ML · H2O (M = Ni,Zn), where LH2 = N,N′-dimethylmonothio-oxamide, have been prepared. The complexes were characterized by metal analyses, thermal methods and spectral (i.r., Raman, u.v.—vis.) studies. The vibrational analyses of the complexes are given using NH/ND, CH3/CD3 and metal isotopic substitutions. The Ni(II), Pd(II), Pt(II) and Cu(II) compounds are square planar. The monoanion LH shows a chelated bidentate S,O-coordination, while the doubly deprotonated L2− acts as a bridging S,N/N,O-tetradentate ligand giving polymeric structures.  相似文献   

3.
A series of hetero ligand MLB complexes (15) were synthesised from tridentate NO2 type Schiff base [H2L: (E)-2-((2-hydroxy-4-methoxyphenyl)(phenyl)methyleneamino)benzoic acid; derived from 2-hydroxy-4-methoxybenzophenone and 2-aminobenzoic acid] and bidentate N2 type 1,10-phenanthroline (B: phen) ligands. The structural characterization of the synthesised MLB complexes were carried out via analytical as well as various spectral studies. Additionally, the low molar conductance values (Λm = 14–22 Ω−1 cm2 mol−1) imply that the complexes (15) are non-electrolytes. The obtained results reinforce that stoichiometry of the mononuclear hetero ligand complexes can be represented as [M(II)-Schiff base(L)-phen(B)·H2O] and both H2L and (B) ligands can act as tri and bidentates respectively. Moreover, both the ligands bind with metal(II) ions to build a stable six, six, five membered chelate rings with octahedral geometry. The existing solvent water molecule is confirmed from thermal as well as vibrational analysis. Their microcrystalline nature and uniform surface morphology were confirmed by both powder XRD and SEM studies. 3D molecular modeling and analysis of NiLB and CuLB complexes (3 and 4) were also studied. Mn(II), Ni(II) and Cu(II) complexes (1, 3 and 4) strongly interact with DNA through intercalation binding with strong binding constant values. The obtained Kapp values were 5.23, 4.98, 6.36, 7.21 and 4.86 × 105 mol−1 for MLB complexes (15) respectively and the negative Δ3G values shown that all the complexes are strongly interact with DNA in a spontaneous manner. Further, remarkable biological, antioxidant and DNA activities were remarkably exhibited by MnLB, NiLB and CuLB complexes.  相似文献   

4.
Mononuclear O,O-coordinated complexes K2(MLCl2) M = Zn(II), Cd(II) and dinuclear complexes (MZnLCl2R2)x along with dinuclear N,N-coordinated complexes (M′ZnH2LCl2R2)y (where M = Zn(II), Cd(II), Hg(II) and M′ = M and Sn(IV); R = Cl, CH3; x = 0, ?2; y = 0, +2) of N′-1-,N′-2-dihydroxy-N-1-,N-2-dipyridin-2-ylethanedimidamide (H2L) have been prepared. All complexes have been characterized by 1H NMR, IR, EI-mass spectroscopy and elemental microanalysis. These results are in agreement with our prediction for structures of mono and dinuclear complexes of H2L and L?2 with Zn(II) in the gas phase by theoretical studies.  相似文献   

5.
The new complexes Pd(SH2)2 · H2O, M(SH) · H2O (M = Ni, Pd, Pt) and M(SH) · 0.5H2O (M = Cu, Zn), where SH3 = N(s)-methylmonothio-oxamide, have been prepared. The complexes were characterized by metal analyses, thermal methods and i.r., Raman and u.v./vis spectroscopic studies. The vibrational analyses of the complexes are given using NH/ND, CH3/CD3 and metal isotopicsubstitutions. The Ni(II), Pd(II), Pt(II) and Cu(II) compounds are square planar. The vibrational spectra show that in Pd(SH2)2 · H2O the coordination occurs via the sulphur atom of the deprotonated thioamide group and the oxygen atom of the neutral primary amide group, in a bidentate chelated fashion. The doubly deprotonated SH2− ion behaves as a bridging bis-bidentate ligand giving polymeric structures.  相似文献   

6.
The redox reaction of bis(2-benzamidophenyl) disulfide (H2L-LH2) with [Pd(PPh3)4] in a 1:1 ratio gave mononuclear and dinuclear palladium(II) complexes with 2-benzamidobenzenethiolate (H2L), [Pd(H2L-S)2(PPh3)2] (1) and [Pd2(H2L-S)2 (μ-H2L-S)2(PPh3)2] (2). A similar reaction with [Pt(PPh3)4] produced only the corresponding mononuclear platinum(II) complex, [Pt(H2L-S)2(PPh3)2] (3). Treatment of these complexes with KOH led to the formation of cyclometallated palladium(II) and platinum(II) complexes, [Pd(L-C,N,S)(PPh3)] ([4]) and [Pt(L-C,N,S) (PPh3)] ([5]). The molecular structures of 2, 3 and [4] were determined by X-ray crystallography.  相似文献   

7.
The i.r. spectra of the complexes M(en)3X2 (M = Mn, Fe, Co, Ni, Cu, Zn), trans-Cu(en)2X2, Ni(en)2X2 and M(en)X2 (M = Ni, Cu, Zn; X = Cl, Br, I) have been studied. Assignments are proposed for the tris(ethylenediamine) complexes on the basis of 15N-, N2D4- and C2D4-labelling of en and the effects of metal ion substitution in relation to our earlier study of [M(en)3]SO4 complexes. Assignments for the bis(ethylenediamine) complexes are based on our observations of halogen-sensitivity and earlier studies on metal isotope labelling and ligand deuteration of the halide complexes and a normal coordinate analysis of the [Cu(en)2]2+ species. The spectra of the halide complexes have been extended below 200 cm−1 for the first time. Finally, the spectra of the mono(ethylenediamine) complexes are discussed in relation to their known or probable structures.  相似文献   

8.
The [M(HL)2(H2O)2]X2 complexes were synthesized (M = Mn(II), Co(II), Ni(II), Cu(II), Zn; X = CH3COO, Cl, BF4 ) that incorporate bidentately coordinated molecules of N,N-dimethylhydrazide of 4-nitrobenzoic acid (HL). The latter molecules chelate the metal atom through the carbonyl O atom and the N atom of dimethylamino group. The square-planar complexes of Cu and Ni with deprotonated form of a ligand with composition ML2 were also isolated. The synthesized complexes were studied by IR, electronic and EPR spectroscopies, and by cyclic voltammetry.  相似文献   

9.
《Polyhedron》1987,6(10):1901-1907
The reaction of a warm ethanolic solution of [Ni(SALSMeTSC-H)Py]Cl·0.5Py (SALSMeTSC = salicylaldehyde S-methylisothiosemicarbazone) with salicylaldehyde and acetylacetone (HACAC), yielded the corresponding square-planar complexes [Ni(SAL2SMeTSC-2H)] (A) and [Ni(SALACACSMeTSC-2H)] (B) (SAL2SMeTSC, and SALACACSMeTSC = quadridentate 2O2N ligand: N(1),N(3)-bis(salicylidene)-S-methylisothiosemicarbazide, and acetylacetone N(1)-salicylidene-S-methylisothiosemicarbazone, respectively). An X-ray analysis of complex B showed that in the reaction of the starting complex with HACAC a rearrangement of the salicylaldehyde moiety takes place (while the CN(3) bond of the azomethine group is ruptured) and its binding to the N(1) nitrogen. At the same time, HACAC is simultaneously bonded to the liberated N(3)-nitrogen of the hydrazine fragment. Crystal data for the complex B (NiC14H15N3O2S) are: Mr = 348.0, orthorhombic, space group Pna21, a = 7.484(3), b = 21.995(8), c = 8.866(3) Å; V = 1459.44 Å3, Z = 4, F(000) = 720, Dc = 1.58 g cm−1, Do = 1.56 g cm−1, μ(MoKα) = 14.45 cm−1. The structure was solved by the heavy-atom method and refined anisotropically to an R value of 0.078 for 1174 non-zero reflections. The complex molecules are planar, the NiNi distance of nearest molecules being about 3.76 Å. The compounds have been characterized by elemental analysis as well as by IR and electronic spectra.  相似文献   

10.
Hydrothermal reactions of V2O5, tetra-2-pyridylpyrazine (tpyprz) and an appropriate M(II) starting material yield a series of oxides of general composition [{Mx(tpyprz)}yV4O12] [x=1, y=2, M=Co(II), Ni(II); x=2, y=2, M=Cu(I); x=2, y=1, M=Zn(II)]. The Co(II) and Ni(II) analogues (1 and 2) are isostructural and consist of one-dimensional ribbons constructed from {V4O12}4− clusters linked through {M(tpyprz)}24+ binuclear units of edge sharing {MO3N3} octahedra. In contrast, the structure of [{Cu2(tpyprz)}2V4O12] (3) is two-dimensional and constructed of {Cu2(tpyprz)}n2n+ chains linked in the second dimension through the {V4O12}4− clusters. The structure of [{Zn2(tpyprz)V4O12] (4) is also two-dimensional but may be described as {Zn2V4O12} chains interconnected through the binucleating tpyprz ligands. The roles of the coordination preferences of the secondary metal cations as well as the nature of the organic components are discussed.  相似文献   

11.
Three new heterometallic complexes, [Cu(N-Meim)4Pd(μ-CN)2(CN)2]n (1), [Zn(N-Meim)3Pd(μ-CN)2(CN)2]n (2) and [Cd(N-Meim)2Pd(μ-CN)4]n (3), have been isolated from the reactions of M[Pd(CN)4] (M = Cu(II), Zn(II) or Cd(II)) and N-Meim (N-methylimidazole) with in different molar ratios. All complexes have been characterized by X-ray analyses, vibrational (FT-IR and Raman) spectra, thermal and elemental analyses. The crystallographic analysis reveals that the crystal structures of 1 and 2 are 1D coordination polymer, while 3 presents a 2D network. In the Cu(II) and Zn(II) complexes, two cyanide groups of [Pd(CN)4]2− coordinated to the adjacent M(II) ions and distorted octahedral and square pyramidal geometries of complexes are completed by four and three nitrogen atoms of N-Meim ligands, respectively. The Cd(II) ion is six-coordinate, completed with the two nitrogen atoms of N-Meim ligands in the axial positions and the four nitrogen atoms from bridging cyano groups in the equatorial plane. The most striking features of complexes 1-3 are the presence of obvious C-H?Pd hydrogen-bonding interactions between the Pd(II) and hydrogen atoms of N-Meim ligand. This weak hydrogen bonding plays a crucial role in the architecture of the network polymers. The adjacent chains are held together by C-H?Pd, C-H?π or π?π interactions, forming three-dimensional network.  相似文献   

12.
《Polyhedron》2007,26(9-11):1787-1792
Two new H-bonding molecular magnets based on [Ni(mnt)2] monoanion have been synthesized and characterized structurally. In crystal of 1, [Ni(mnt)2] monoanions form the π-stacked sheets and the neighboring anionic sheets are held together via H-bonding interactions between –NH groups of diprotonated benzene-1,4-diamine and CN groups of mnt2− ligands. In crystal of 2, the neighboring anionic dimers form an anionic column via Ni…S contacting interactions, and these anionic stacks arrange into a sheet which is parallel to crystallographic ab-plane. The H-bonding interactions between diprotonated 1,4-diazabicyclo[2.2.2]octane cations and [Ni(mnt)2] monoanions as well as between cations and solvent MeCN molecules stabilize the lattice. Magnetic susceptibility measurement for 1 indicates an activated magnetic behavior in the high-temperature range together with a Curie tail at the lower temperature range, but the magnetic feature deviates from the magnetic exchange model for a spin dimer with S = 1/2. The magnetic nature of 2 reveals the presence of strongly antiferromagnetic interactions between the nearest-neighboring spins, the larger energy gap between spin ground and excited states results in a weakly paramagnetic property.  相似文献   

13.
Eight new heterodinuclear Cu(II)–M(II) (M = Pb and Zn) complexes of four new phenol based compartmental macrocyclic ligands, possessing contiguous (N2O2) and (NxO2) (x = 2, 3) coordination sites, were prepared by the template reaction of [N,N′-bis(3-formyl-5-methylsalicylidene)ethane-1,2-diaminato]copper(II), with various di- and/or tri-amines in the presence of Pb(II) and Zn(II) ions. The crystal structure of [CuZnL3(H2O)](ClO4)2, 6, was determined by X-ray diffraction and shows that the Zn(II) and Cu(II) ions reside in the N2O2 sites of the macrocyclic ligand. The fifth coordination site of the Zn centre is occupied by a water ligand. All the complexes have been characterized by elemental analysis, molar conductivity and spectroscopic methods (IR and UV). Also, all the synthesized complexes were screened for their antibacterial and antifungal activity against Escherichia coli, Staphyloccocus aureus and Candida albicans.  相似文献   

14.
In this study, the novel vic-dioxime ligand (3) and its Ni(II), Cu(II), Co(II), Cd(II) and Zn(II) complexes (48) were synthesized for the first time by condensation reactions of N-(4-aminophenyl)aza-15-crown-5 (1) and anti-chlorophenylchloroglyoxime (2). All of these new compounds were characterized by the elemental analysis, Fourier transform infrared, ultraviolet–visible, mass spectrometry, 1H NMR, 13C NMR and magnetic susceptibility measurements. The electrochemical properties of the ligand and its complexes have been investigated by cyclic voltammetry at the glassy carbon electrode in 0.1 M TBATFB in DMSO.  相似文献   

15.
《Polyhedron》2002,21(14-15):1429-1437
N-Benzoylthioureas have been reported to form complexes with gold (III) and palladium (II) and other transition metals. In this study, an N-benzoyl-N′,N′-diethylthiourea (3f) ligand was used in the solvent extraction of palladium(II) and gold(III) from aqueous chloride media (0.1 mol l−1 NaCl). The distribution coefficient was determined as a function of both metal concentration in the aqueous phase and extractant concentration in the organic phase. The experimental distribution data were numerically analysed by letagrop-distr software in order to obtain the thermodynamic model corresponding to the metal extraction. It is found that pH does not affect the metal extraction process in the 1–2 pH range. Synthesis of the palladium benzoyl thiourea complexes was carried out by mixing quantities of metal and ligand solutions in methanol in a 1:2 ratio stoichiometric. Yields of 74 and 80.9% were obtained for the Pd-3c and Pd-3f complexes. In order to confirm the formation of the palladium complexes, NMR, FTIR and MS analyses were performed. From MS analyses a complex stoichiometry 1:2 (metal:ligand) was confirmed. The formation of crystals of palladium N-benzoyl-N′,N′-diethylthiourea complex (Pd-3f) in the methanolic solution allows the characterisation of the complex structure by XRD. The resulting structure is described and discussed. Bis(1,1,-diheptadecyl-3-benzoyl-thioureate)palladium(II) (Pd-3c) and bis(1,1,-diheptadecyl-3-benzoyl-thioureate)palladium(II) (Pd-3f) were used as ionophores in polymeric membrane electrodes. Their potentiometric responses to different anionic metal chlorocomplexes are evaluated and discussed taking into consideration the results obtained in the liquid–liquid distribution studies. A nernstian response was only obtained for AuCl4  (PDL=8.8×10−8) and PdCl4 2− (PDL=1.5×10−4 M) with a selectivity coefficient of KAuCl4-, PdCl42−pot=−3.4, calculated taking AuCl4  as being the primary anion.  相似文献   

16.
The complexes M(L1, 2)2 · nH2O, where M = Co(II), Ni(II), Cu(II), and Zn; n = 2 and 3, were synthesized by the reaction of Co(II), Ni(II), Cu(II), and Zn(II) chlorides with 2,4,7-trinitro-9-fluorenone oxime (HL1) and 2,4,5,7-tetranitro-9-fluorenone oxime (HL2) and identified. It was shown that HL1, 2 were coordinated by metal cations in the anionic form in a 2: 1 ratio. A single crystal of the solvate of HL2 with acetonitrile (1: 1) HL2 · NCCH3 was isolated, and its crystal structure was determined. The spectral characteristics were determined, and the acidity constant of HL1 was calculated. The structures for the synthesized complexes were proposed.  相似文献   

17.
Four 1:1, two-component salts combining the [Ni(dmit)2] anion (dmit2− = 2-thioxo-1,3-dithiole-4,5-dithiolato) and chiral stilbazolium-based countercations (HPMS+ = 4′-[2-(hydroxymethyl)pyrrolidinyl]-1-methylstilbazolium and MPMS+ = 4′-[2-(methoxy-methyl)pyrrolidinyl]-1-methylstilbazolium), or chiral ferrocenyl-based countercations (2+ = (E)-1-((R)-2-methylferrocenyl)-2-(1-methyl-4-pyridiniumyl)ethene; 3+ = (E)-1-((S)-2-trimethylsilylferrocenyl)-2-(1-methyl-4-pyridiniumyl)ethene) were prepared. Semiconducting behaviour (2·10−4 S·cm−1 measured on compressed pellets for [Ni(dmit)2] (MPMS), for example) is secured by the presence of the [Ni(dmit)2] anions. The chiral nature of the countercations ensures non-centrosymmetry of the structures (space group P1 for [Ni(dmit)2](2) and [Ni(dmit)2](3), for example). A ubiquitous antiparallel arrangement of the cations, which are thus packed in a pseudo-centrosymmetrical environment, results in almost vanishing second-order susceptibilities χ(2), and therefore zero efficiencies in second harmonic generation.  相似文献   

18.
Three Co(II), Ni(II) and Zn(II) complexes of orotate with the N-methylimidazole ligand were synthesized and characterized by means of elemental and thermal analysis, magnetic susceptibilities, IR, UV-Vis spectroscopic and antimicrobial activity studies. The crystal structures of [Co(HOr)(H2O)2(Nmeim)2]3·H2O (1), [Ni(HOr)(H2O)2(Nmeim)2] (2) and [Zn(HOr)(H2O)(Nmeim)2] (3) were determined by the single crystal X-ray diffraction technique (H3Or = orotic acid and Nmeim = N-methylimidazole). In complexes 1 and 2, the Co(II) and Ni(II) ions have distorted octahedral geometries with two Nmeim, one orotate and two aqua ligands. Complex 3 has a distorted trigonal bipyramidal geometry with two N-methylimidazole, one orotate and one aqua ligands. In the complexes, the orotate is coordinated to the metal(II) ions through the deprotonated nitrogen atom of the pyrimidine ring and the oxygen atom of the carboxylate group as a bidentate ligand. The complexes form a three-dimensional framework by hydrogen bonding, C-H?π and π?π stacking interactions. The MIC values of the complexes against selected microorganisms were determined to be in range 300-2400 μg/mL.  相似文献   

19.
Metal(II) complexes of N-(thiophene-2-carboxamido)salicylaldimine (H2TCS) of types M(H2TCS)2Cl2 [M = Ni, Cu and Zn], M(HTCS)Cl [M = Co, Ni and Cu], M(HTCS)2 [M = Mn, Fe, Co, Ni, Cu and Zn], M(TCS)·xH2O [M = Mn, Co and Ni, x = 2; M = Cu, x = 0], Ni(TCS)py2 and Cu(TCS)py have been prepared. Elemental analyses, molar conductance, magnetic moment, electronic, IR and ESR spectral studies have been used to characterize these complexes. The different modes of chelation of the ligand and the stereochemistry of the complexes are discussed.  相似文献   

20.
The solvent-free conditions were employed to synthesise symmetrical Schiff base ligand from 2,6-diaminopyridine with cinnamaldehyde in (1 min) with a fair yield utilizing formic acid as a catalyst. Through coordination chemistry, new heteroleptic complexes of Cu(II), Co(II), Ni(II), Pt(II), Pd(II) and Zn(II) were achieved from Schiff base as a primary chelator (L1) and 2,2′‐bipyridine (2,2′-bipy) as a secondary chelator (L2). The prepared compounds have been characterized by elemental analysis, molar conductivity, magnetic susceptibility, FTIR, 1H NMR, UV–visible, mass spectrometry, and thermal gravimetric analysis, and screened in vitro for their potential as antibacterial activity by the agar well diffusion method. The metal complexes were formulated as [M (L1) (L2) (X)] YnH2O, L1 = Schiff base, L2 = 2,2′-bipy, (M = Cu(II), Co(II), Zn(II), Y = 2NO3, n = 1), (M = Ni(II), X = 2H2O, Y = 2NO3, n = 0) and (M = Pd(II) Pt(II), Y = 2Cl, n = 0). Both L1 and L2 act as a neutral bidentate ligand and coordinates via nitrogen atoms of imine and 2,2′-bipy to metal ions. The metal complexes were found to be electrolytic, with square-planar heteroleptic Cu(II), Co(II), Pt(II), and Pd(II) chelates and octahedral Ni(II) complex. As well as tetrahedral geometry, has been proposed for the complex of Zn(II). Furthermore, the biological activity study revealed that some metal chelates have excellent activity than Schiff base when tested against Gram-negative and Gram-positive strains of Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). Finally, it was found that the Zn(II) and Pd(II) complexes were more effective against both types of bacteria tested than the imine and other metal complexes.  相似文献   

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