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1.
Reactions of Ni(NO3)2 · 6H2O) in EtOH(iso-PrOH) with optically active bis(menthane) ethylene-diaminodioxime (H2L1), pinano-para-menthane ethylenediaminodioxime (H2L2), pinano-para-menthane propylenediaminodioxime (H2L3) and bis(pinane) propylenediaminodioxime (H2L4) were used to synthesize [Ni(H2L1)NO3[NO3 · 2H2O (I), [Ni(HL2)]NO3 (II), [Ni(HL3)]NO3 (III), and [Ni(HL4)]NO3 (IV). X-ray diffraction study of paramagnetic complex Ieff = 3.04 μB and diamagnetic complexes II and III revealed their ionic structures. A distorted octahedral polyhedron N4O2 in the cation of complex I is formed by the N atoms of tetradentate cycle-forming ligand, i.e., the H2L1 molecule, and the O atoms of the NO 3 ? anion acting as a bidentate cyclic ligand. In the cations of complexes II and III, containing a pinane fragment, the coordination core NiN4 has the shape of a distorted square formed on coordination of tetradentate cycle-forming ligands, i.e., anions of the starting dioximes. The structure of diamagnetic complex IV is likely to be similar to the structures of complexes II and III.  相似文献   

2.
The homonuclear water-soluble and air stable compounds (dmpH) (H5O2) au][M(pydc)2].0.5H2O (M = Ni(II) (1), Cu(II) (2), Zn(II) (3); pydcH2 = pyridine-2,6-dicarboxylic acid, dipicolinic acid, dmp = 2,9-dimethyl-1,10-phenanthroline) have been prepared by self-assembly synthesis in aqueous solution at room temperature, and characterized by IR, 1H NMR, 13C NMR, elemental analysis and X-ray diffraction single crystal analyses for 1, 2 and 3. The complexes 1–3 represent the isostructural features. Extensive hydrogen bonding interactions involving all aqua ligands, dipicolinate oxygens and lattice water molecules further stabilize the complex units by linking them to form three dimensional polymeric networks. The stoichiometry and stability of the all three complexes in aqueous solution were investigated by potentiometric pH titration.  相似文献   

3.
Four new coordination complexes of palladium(II) and platinum(IV) starting from bis(dimethylthiocarbamoyl)sulphide (L1) and bis(diethylthiocarbamoyl)disulphide (L2) were synthesized and characterized in solid state by elemental analysis, infrared and electronic spectroscopy as well as thermal analysis (TG/DTA). The complexes were formulated on the basis of experimental data as [Pd(Me2NCS2)2] (1), [Pt(Me2NCS)2SCl4]·3H2O (2), [Pd(Et2NCS2)2] (3) and [Pt(Et2NCS)2S2Cl4]·4H2O (4), respectively. TG experiments revealed the nature of complex species as hydrated (2 and 4) or anhydrous (1 and 3). Thermal decomposition of coordinated organic ligands occurs in one or two exothermic stages, the final residue being in all cases the free metal (Pd or Pt).  相似文献   

4.
Two new isomorphous coordination polymers [Co(4,4′-Bpda)(Dpa)] n (I) and [Ni(4,4′-Bpda)(Dpa)] n · H2O (II) (4,4′-H2Bpda = benzophenone-4,4′-dicarboxylic acid, Dpa = dipyridin-4-ylamine) were synthesized under solvothermal condition and characterized by elemental analysis, FT-IR and single-crystal X-ray diffraction technique. Compounds I and II exhibit 2D helical layers resulting from alternating single helical chains and double helical chains, which feature uninodal 4-connected topology with a point symbol of 66.  相似文献   

5.
Anhydrous and partially hydrated acid trinuclear trifluoroacetates of divalent transition metals of the composition [M3(CF3COO)6(CF3COOH)6)](CF3COOH) and [M3(CF3COO)6(CF3COOH)2(H2O)4)](CF3COOH)2, respectively, where M = Co (I, III) Ni (II, IV), were synthesized and studied by X-ray diffraction. Complexes I and II were obtained by crystallization from solutions of M(CF3COO)2 · 4H2O in trifluoroacetic anhydride; complexes III and IV were synthesized under the same conditions with the use of 99% trifluoroacetic acid as a solvent. Crystals I are triclinic: space group $P\bar 1$ , a = 13.199(6) Å, b = 14.649(6) Å, c = 15.818(6) Å, α = 90.04(4)°, β = 114.32(4)°, γ = 108.55(4)°, V = 2611.3(19) Å3, Z = 2, R = 0.0480. Crystals II are trigonal: space group $R\bar 3$ , a = 13.307(2) Å, c = 53.13(1) Å, V = 8148(2) Å3, Z = 6, R = 0.1112. Crystals III are triclinic: space group $P\bar 1$ , a = 9.001(8) Å, b = 10.379(9) Å, c = 12.119(9) Å, α = 83.67(5)°, β = 72.33(5)°, γ = 83.44(5)°, V = 1068.3(15) Å3, Z = 1 Å, R = 0.1031. Crystals IV are triclinic: space group $P\bar 1$ , a = 9.121(18) Å, b = 10.379(2) Å, c = 12.109(2) Å, α = 84.59(3)°, β = 72.20(3)°, γ = 82.80(3)°, V = 1080.94(40) Å3, Z = 1, R = 0.0334.  相似文献   

6.
Nickel(II) and copper(II) complexes of two unsymmetrical tetradentate Schiff base ligands [Ni(Me-salabza)] (1), [Cu(Me-salabza)] (2) and [Ni(salabza)] (3), {H2salabza = N,N′-bis[(salicylidene)-2-aminobenzylamine] and H2Me-salabza = N,N′-bis[(methylsalicylidene)-2-aminobenzylamine]}, have been synthesized and characterized by elemental analysis and spectroscopic methods. The crystal structures of 2 and 3 complexes have been determined by single crystal X-ray diffraction. Both copper(II) and nickel(II) ions adopt a distorted square planar geometry in [Cu(Me-salabza)] and [Ni(salabza)] complexes. The cyclic voltammetric studies of these complexes in dichloromethane indicate the electronic effects of the methyl groups on redox potential.  相似文献   

7.
Complexes of three related 1-azapentadienyl ligands [N(SiMe2R1)C(But)(CH)3SiMe2R], abbreviated as L (R = But, R= Me), L′ (R = Me = R1), and L″ (R = But = R1), are described. The crystalline compounds Sn(L)2 (1), Sn(L′)2 (2), [Sn(L′)(μ-Cl)]2 (3) and [Sn(L″)(μ-Cl)]2 (4) were prepared from SnCl2 and 2 K(L), 2 K(L′), K(L′) and K(L″), respectively, in thf. Treatment of the appropriate lithium 1-azapentadienyl with Si(Cl)Me3 yielded the yellow crystalline Me3Si(L) (5) and the volatile liquid Me3Si(L′) (6) and Me3Si(L″) (7), each being an N,N,C-trisilyldieneamine. The red, crystalline Fe(L)2 (8) and Co(L′)2 (9) were obtained from thf solutions of FeCl2 with 2 Li(L)(tmeda) and CoCl2 with 2 K(L′), respectively. Each of 1-9 gave satisfactory C, H, N analyses; 6 and 7 (GC-MS) and 1, 2, 8 and 9 (MS) showed molecular cations and appropriate fragments (also 3 and 4). The 1H, 13C and 119Sn NMR (1-4) and IR spectra support the assignment of 1-4 as containing Sn-N(SiMe2R1)-C(But)(CH)3SiMe2R moieties and 5-7 as N(SiMe3)(SiMe2R1)C(But)(CH)3SiMe2R molecules; for 1-4 this is confirmed by their X-ray structures. The magnetic moments for 8 (5.56 μB) and 9 (2.75 μB) are remarkably close to the appropriate Fe and Co complex [M{η3-N(SiMe3)C(But)C(H)SiMe3}2]; hence it is proposed that 8 and 9 have similar metal-centred, centrosymmetric, distorted octahedral structures.  相似文献   

8.
Coordination equilibrium constants (K NiS) of some donor solvent molecules to 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecanenickel(II) ([Ni(Me4[12]aneN4)]2+) were determined in nitrobenzene (a noncoordinating bulk solvent). The first (K NiS1) and second stepwise coordination equilibrium constants (K NiS2) for 1,4,7,10-tetraazacyclododecanenickel(II) ([Ni([12]aneN4)]2+), 1,4,8,11-tetraazac yclotetradecane- nickel(II) ([Ni([14] aneN4)]2+), 1,4,8,11-tetrathiacyclotetra-decanenickel(II) ([Ni([14]aneS4)]2+) were also reinvestigated. The K NiS values for [Ni(Me4[12]aneN4)]2+ were compared to those of [Ni([12]aneN4)]2+, (1R,4S, 8R,11S)-1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecanenickel(II) (R,S,R,S-[Ni(Me4[14]aneN4)]2+), R,R,S,S-[Ni(Me4[14]aneN4)]2+, [Ni([14]aneN4)]2+, and [Ni([14]aneS4)]2+. Coordination of pyridine (Py), N,N,N′,N′-tetramethylurea (TMU), and N,N-dimethylacetamide (DMA) to [Ni(Me4[12]aneN4)]2+ was observed, although these donor solvent molecules did not coordinate to R,S,R,S-[Ni(Me4[14]aneN4)]2+. The K NiS values for Py, TMU, and DMA are 7.9, 2.8, and 9.0 dm3⋅mol−1, respectively. Some hydrogen-bonding waters were coordinated to R,S,R,S-[Ni(Me4[14]aneN4)]2+, but such waters did not coordinate to [Ni(Me4[12] aneN4)]2+. Also, the K NiS2 values were larger than the corresponding K NiS1 values for [Ni([14]aneS4)]2+. Furthermore, the K NiS1 values for [Ni([12]aneN4)]2+ were the largest among these nickel(II) complex cations. The K NiS, K NiS1, and K NiS2 values are discussed in terms of properties of the donor solvents and steric strains of these nickel(II) complex cations.  相似文献   

9.
Three new binuclear Ni(II) complexes [{Ni(L22py)Cl}2](ClO4)2 (1), [{Ni(L23py)Cl}2](ClO4)2 (2), and [{Ni(L33py)Cl}2](ClO4)2 (3), {L22py = N-(2-pyridylmethyl)-N-(2-aminoethyl)-1,2-diaminoethane, L23py = N-(2-pyridylmethyl)-N-(2-aminoethyl)-1,3-diaminopropane, L33py = N-(2-pyridylmethyl)-N-(3-aminopropyl)-1,3-diaminopropane} have been synthesized. Single crystal X-ray structure analysis showed that in each complex two distorted octahedral Ni(II) ions are bridged asymmetrically by a pair of chloride anions. Variable temperature magnetic susceptibility measurements of 1 and 3 revealed dominant ferromagnetic exchange interactions.  相似文献   

10.
A series of tricarbonyl rhenium(I) and manganese(I) complexes of the electroactive 2-(pyrazolyl)-4-toluidine ligand, H(pzAnMe), has been prepared and characterized including by single crystal X-ray diffraction studies. The reactions between H(pzAnMe) and M(CO)5Br afford fac-MBr(CO)3[H(pzAnMe)] (M = Mn, 1a; Re, 1b) complexes. The ionic species {fac-M(CH3CN)(CO)3[H(pzAnMe)]}(PF6) (M = Mn, 2a; Re, 2b) were prepared by metathesis of 1a or 1b with TlPF6 in acetonitrile. Complexes 1a and 1b partly ionize to {M(CH3CN)(CO)3[H(pzAnMe)]+}(Br) in CH3CN but retain their integrity in less donating solvents such as acetone or CH2Cl2. Each of the four metal complexes reacts with (NEt4)(OH) in CH3CN to give poorly-soluble crystalline [fac-M(CO)3(μ-pzAnMe)]2 (M = Mn, 3a; Re, 3b). The solid state structures of 3a and 3b are of centrosymmetric dimeric species with bridging amido nitrogens and with pyrazolyls disposed trans- to the central planar M2N2 metallacycle. In stark contrast to the diphenylboryl derivatives, Ph2B(pzAnMe), none of the tricarbonyl group 7 metal complexes are luminescent.  相似文献   

11.
The ability of heterometallic Ge(IV) and Sn(IV) complexes [Co(H2O)6][Ge(HCitr)2] (I), [Co(H2O)6] [Sn(HCitr)2] (II), [Ni(H2O)6][Ge(HCitr)2] (III), [Ni(H2O)6][Sn(HCitr)2] (IV), [Mg(H2O)6][Ge(HCitr)2] (V), and [Mg(H2O)6][Sn(HCitr)2] (VI) (H4Citr is citric acid) to activate polycondensation of maleic and phthalic anhydrides with ethylene glycol was studied. Copolymerization of modified poly(glycol maleate phthalate) with triethylene glycol dimethacrylate was performed, and the copolymer characteristics were determined.  相似文献   

12.
Two new complexes [Co(NIT-1′-MeBzIm)2(Dca)2] (I) and [Ni(NIT-1′-MeBzIm)2(Dca)(H2O) · NO3 · H2O (II) (NIT-1′-MeBzIm = 2-{2′-[(l′-methyl)benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide; Dca = N(CN)2) were prepared and structurally characterized by single-crystal X-ray diffraction. Relevant crystallographic parameters are as follows: monoclinic, P21/c space group, Z = 4; crystal data: C34H38N14O4Co, M = 765.71, a = 14.343(4), b = 14.322(4), c = 18.626(5) Å, β = 105.956(3)° for I. Orthorhombic Pna21 space group, Z = 4; crystal data: C32H42N12O9Ni, M = 797.49, a = 24.426(4), b = 11.0326(18), c = 13.980(2)Å for II. The X-ray analysis reveals that Co2+ ion and Ni2+ ion resides in a approximate sdistorted octahedron center. In I, the complex was linked by intermolecular hydrogen bonds, resulting in a 1D chain configuration. In II, the complex was linked by intermolecular hydrogen bonds, resulting in a 2D network configuration.  相似文献   

13.
The reactions of a racemic four-coordinate Ni(II) complex [Ni(rac-L)](ClO4)2 with l- and d-alanine in acetonitrile/water gave two six-coordinate enantiomers formulated as [Ni(RR-L)(l-Ala)](ClO4)·2CH3CN (1) and [Ni(SS-L)(d-Ala)](ClO4) (2) (L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclo-tetradecane, Ala? = alanine anion), respectively. Evaporation from the remaining solutions gave two four-coordinate enantiomers characterized as [Ni(SS-L)](ClO4)2 (S-3) and [Ni(RR-L)](ClO4)2 (R-3), respectively. Single-crystal X-ray diffraction analyses of complexes 1 and 2 revealed that the Ni(II) atom has a distorted octahedral coordination geometry, being coordinated by four nitrogen atoms of L in a folded configuration, plus one carboxylate oxygen atom and one nitrogen atom of l- or d-Ala? in mutually cis-positions. Complexes 1 and 2 are supramolecular stereoisomers, constructed via hydrogen bonding between [Ni(RR-L)(l-Ala)]+ or [Ni(SS-L)(d-Ala)]+ monomers to form 1D hydrogen-bonded zigzag chains. The homochiral natures of complexes 1 and 2 have been confirmed by CD spectroscopy.  相似文献   

14.
The reaction of Gd(BH4)3(THF)2 with two equivalents of sodium N,N′-dicyclohexyl-N″-bis(trimethylsilyl)guanidinate in THF followed by the treatment of the reaction product with 1,2-dimethoxyethane produced the monoguanidinate bis(borohydride) complex [(Me3Si)2NC(NCy)2]Gd(BH4)2DME (1) (Cy is cyclohexyl). The treatment of the heterobimetallic samarium complex {(Me3Si)2NC(NPri)2}2Sm(BH4)2Li(THF)2, in which the lanthanide and lithium atoms are linked by two bridging borohydride groups, with 1,2-dimethoxyethane afforded the ionic complex [{(Me3Si)2NC(NPri)2}2Sm(BH4)2]?[Li(DME)3]+ (2). The structures of complexes 1 and 2 were established by X-ray diffraction. The [(Me3Si)2NC(NCy)2]2Ln(BH4)2Li(THF)2 complexes (Ln = Nd (3), Sm (4), or Yb (5)) were found to catalyze methyl methacrylate polymerization.  相似文献   

15.
Five structural kinds of nickel hydrogen-bonded networks containing hydrotris(3,5-dimethylpyrazolyl)borate ligands (Tp) have been elucidated by X-ray diffraction, [TpNi(OH2)3][(p-NO2C6H4O)2PO2] (4), [TpNi(OH2)3][Me2PO2]·Me2P(O)OH (5), [TpNi(OH2)3][(nBuO)2PO2]·0.5H2O (6), [(Hpz)TpNi(OH2)2][(Ph)PO2OH] (7) and [TpNi(OH2)2(Me2PO2)] (8). The most relevant supramolecular feature of complexes 4-8 is all of them form coordination networks based on hydrogen bonds between water molecules and phosphate, phosphonate or phosphinate anions. These hydrogen bonds are formed within the monomer units in addition to connect monomers along the chains. Their behaviors in solution were investigated by one- and two-dimensional 1H NMR techniques.  相似文献   

16.
A series of six organotin(IV) carboxylates [Me2SnL2] (1), [n-Bu2SnL2] (2), [n-Oct2SnL2] (3), [Me3SnL] (4), n-Bu3SnL (5) and [Ph3SnL] (6), where L = 3-(4-cyanophenyl) acrylic acid have been synthesized and characterized by elemental analysis, FT-IR and NMR (1H, 13C). The complex (4) was also analyzed by single crystal X-ray analysis which showed distorted trigonal bipyramidal geometry with polymeric bridging behavior. The complexes 16 were screened for antimicrobial activities and cytotoxicity. The results showed significant activity with few exceptions. The catalytic activity of complexes was assessed in transesterification reaction of Brassica campestris oil (triglycerides) to produce biodiesel (fatty acid methyl esters). The results showed that triorganotin(IV) complexes exhibited good catalytic activity than their di-analogues.  相似文献   

17.
Copper(II) salts were reacted with various quinoline aldehyde chalcogensemicarbazones to yield compounds formulated as Cu(HL)X2 · nH2O (I: HL = quinoline aldehyde thiosemicarbazone (HL1), X = ClO4, n = 2; II: HL = quinoline aldehyde 4-C2H5-thiosemicarbazone (HL1a), X = NO3, n = 0; III: HL = quinoline aldehyde semicarbazone (HL2), X = ClO4, n = 3 and IV: HL = quinoline aldehyde 4-Ph-semicarbazone (HL2a), X = NO3, n = 1). Regardless of the reagent ratio, the products were compounds having the metal: ligand ratio of 1: 1, where the organic ligand was coordinated tridentate in a molecular form. Single-crystal X-ray diffraction showed that, depending on the chalcogen atom in the organic ligand (S or O), the substituent in the 4th position (at the terminal nitrogen atom), and the specifics of the acido ligand, complexes I–IV had appreciably differing molecular structure organizations. The structures of I and III are formed by a 1D charged coordination polymer, ClO 4 ? anions, and water molecules and may be described by the formula [Cu(HL)(H2O)(ClO4)] n (ClO4) n · nH2O. Copper(II) coordination polyhedra in I and II are (4 + 2) and (4 + 1 + 1) tetragonal bipyramids, respectively. In II and IV, the structures are monomeric and can be described as [Cu(HL1a)(NO3)2] with the metal coordination polyhedron shaped as a (4 + 1) tetragonal pyramid in II and as [Cu(HL2a)(H2O)(NO3)](NO3) with the metal coordination polyhedron shaped as a (3 + 2) trigonal bipyramid in IV. The structure of II is built of molecular complexes, each comprising, apart from ligand HL1a, two monodentate coordinated NO 3 ? groups. The oxygen atom of one anion together with the NNS donor atom set of ligand HL1a form the base, and the oxygen atom of the other anion is in the apex of the coordination polyhedron. In IV, the structure is ionic and built of NO 3 ? anions and [Cu(HL2a)(H2O)(NO3)]+ complex cations, where a cationic coordination polyhedron has a trigonal-bipyramidal configuration with organic ligand HL2a positioned along the long edge. The bipyramidal base is made up by the oxygen atoms of the coordinated water molecule and monodentate nitrato group and the nitrogen atom N2 of the azomethyne group.  相似文献   

18.
Three new coordination polymers, [Mn(BDC-F4)(DMF)2(H2O)2] n (1), [Ni(BDC-F4)(DMF)(EtOH)] n (2), and [Cd(BDC-F4)(DMF)(EtOH)] n (3), have been synthesized by assembling transition metal salts with the rigid ligand tetrafluoroterephthalic acid (H2BDC-F4) in mixed EtOH/DMF solvent at pH ca. 2. For complex 1, the octahedral coordination geometry of the MnII center is provided by two oxygen atoms from two dianionic BDC-F4 ligands, two DMF ligands and two aqua ligands, giving a 1-D linear chain array. For complex 2, the NiII center is coordinated by two dianionic BDC-F4 ligands, two EtOH ligands and two DMF ligands, resulting in a 1-D chain structure. For complex 3, the CdII center is coordinated by four dianionic BDC-F4 ligands, one EtOH ligand and one DMF ligand, generating a 2-D layered structure. The results suggest that both the metal and the solution pH play an important role in the formation of the complexes. The spectroscopic, thermal, and luminescence properties of the complexes have been investigated.  相似文献   

19.
The Ni(II) complexes [Ni(L)2](ClO4)2 (1) and [Ni(L)2(NO3)2] (2), where L is the Schiff base ligand of 4,5,9,13,14-pentaaza-benzo[b] triphenylene, were synthesized and characterized by physico-chemical and spectroscopic methods. Nano-sized particles of (1) were prepared both by sonochemistry (3) and solvothermal (4) methods. NiO nanoparticles were obtained by calcination of the nano-structure complexes at 500 °C. The structures of the nano-sized compounds were characterized by X-ray powder diffraction and scanning electron microscopy. The thermal stabilities of the bulk complexes (1–2) and nano-sized particles (3–4) were studied by thermogravimetric and differential scanning calorimetry. The catalytic activities of complexes of (1–4) are reported. The free Schiff base and its Ni(II) complexes have been screened for antibacterial activities against three Gram-positive bacteria. The metal complexes are more active than the free Schiff base. Electrochemical studies show that the Ni complexes undergo irreversible reduction in MeCN solution.  相似文献   

20.
Three new complexes, [CdL2(CH3COO)2(H2O)2] (I), CdL2Br2 (II), CdL2I2 (III), have been successfully synthesized by self-assembly of corresponding metal salts with (E)-2-(3-(4-(1H-imidazole-1-yl)styryl)-5,5-dimethylcyclohex-2-enylidene)malononitrile (L). The structures of the complexes were determined by single crystal X-ray diffraction analysis (CIF file CCDC nos. 957831 (I), 957792 (II), 957832 (III)). In complex I, central metal is six-coordinated and the crystal packing shows a 3D supramolecular framework. Complexes II and III display the similar 2D supramolecular structures in which the central metals are four-coordination. The luminescent properties were investigated.  相似文献   

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