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1.
Alkylation of ethylenediamine with allyl bromide in the presence of NaHCO3 in benzene-ethanol and acetone-ethanol gave N,N,N′,N′-tetraallylethylenediamine L4 and N,N,N,N′,N′-pentaallylethylenediaminium bromide (L5(H+)Br2), respectively. The ac electrochemical synthesis at copper wire electrodes in solutions of copper(II) halide and an appropriate ligand yielded single crystals of Cu(I) complexes with ethylenediaminium ([L0(H+)2]0.5CuCl2 (I) and [L0(H+)2]0.5CuBr1.67Cl0.33 (II)) and its N-allyl derivatives N,N,N′,N′-tetraallylethylenediaminium ([{L4(H+)2}0.5Cu2Cl3] (III)) and N,N,N,N′,N′-pentaallylethylenediaminium ([L5(H+)Cu4Br6] (IV)). The crystal structures of complexes I–IV were determined by X-ray diffraction. The isostructural crystals of complexes I and II are triclinic, space group P $ \bar 1 $ , Z = 2. For I: a = 5.936(3), b = 6.387(3), c = 7.126(4) Å, α = 67.82(4)°, β = 72.98(4)°, γ = 67.55(4)°, V = 227.7(2) Å3. For II a = 6.110(3), b = 6.657(3), c = 7.309(3) Å, α = 68.40(3)°, β = 72.38(3)°, γ = 67.23(3)°, V = 250.4(2) Å3. In structures I and II, the organic cations are between infinite anionic chains (Cu 2 ? ) n . The crystals of π-complex III are triclinic, space group P $ \bar 1 $ , a = 6.851(4), b = 8.729(4), c = 9.960(4) Å, α = 98.25(3)°, β = 102.29(3)°, γ = 107.30(3)°, V = 541.8(5) Å3, Z = 2. In structure III, all the four allyl groups are π-coordinated by the metal atoms of four discrete anions Cu4Cl 6 2? . The crystals of π-complex IV are monoclinic, space group C2/c, a = 15.228(5), b = 17.095(6), c = 20.182(6) Å, β = 92.43(4)°, V = 5249(3) Å3, Z = 8. Only two of five allyl groups at the same N atom are coordinated by copper(I) atoms. Structure IV contains a complex inorganic fragment of the formula (Cu4Br 6 2? ) n .  相似文献   

2.
Crystals of the -complex [C4H8N2(C3H5)4]2+[CuCl2] 2 (I) were prepared by ac electrochemical synthesis from copper and N,N,N,N-tetraallylpiperasinium chlorides in alcohol solution. Similar synthesis with the use of the metal and N,N,N,N-tetraallylpiperasinium bromides yielded the complex [C4H8N2(C3H5)4]2+[CuBr3]2– (II). Structures I and II were studied by X-ray diffraction (DARCh automated single-crystal diffractometer, MoK radiation). Crystals of I are triclinic, space group P1¯, a = 8.650(3) Å, b = 7.572(2) Å, c = 8.095(3) Å, = 100.45(2)°, = 83.91(2)°, = 99.89(2)°, V = 512.1(6) Å3, Z = 1. Crystals of II are orthorhombic, space group Pn21 a, a = 17.673(3) Å, b = 14.369(6) Å, c = 8.244(2) Å, V = 2093(2) Å3, Z = 4. In structure I, the potentially tetradentate N,N,N,N-tetraallylpiperasinium cation uses two centrosymmetric allyl groups for bonding with copper atoms, whose environment is completed to the trigonal-planar coordination with the chlorine atoms. The [C4H8N2(C3H5)4]2+[CuCl2] 2 groups are joined into a three-dimensional framework by weak hydrogen bonds. The inorganic fragment CuCl 2 is partially disordered, which appears as splitting of the positions of the copper atom and one of the chlorine atom. In compound II, the inorganic fragment occurs as an unusual trigonal-planar CuBr2– 3 anion; the N,N,N,N-tetraallylpiperasinium cation is not involved in metal coordination.  相似文献   

3.
Mercury(II) complexes of 1,10-phenanthroline (phen) and 2,2′-bipyridine (bipy), [Hg(phen)2(SCN)2] (1), [Hg(2,2′-bipy)2(SCN)2] (2) and [Hg(phen)2(NO3)2] (3) have been synthesized and characterized by elemental analysis, IR, 1H NMR and 13C NMR spectroscopy. The thermal stability of 13 were studied by thermal gravimetric (TG) and differential thermal analyses (DTA). The structure of 1 has been confirmed by X-ray crystallography. The complex is a monomer and the Hg atom has an unsymmetrical six-coordinate geometry, formed by four nitrogen atoms of the two phen ligands and two sulfur atoms of the two thiocyanate anions. Solid-state luminescent spectra of phen, 2,2′-bipy and 13 indicate emission with the maximum intensity at ca 467 nm upon excitation at 295 nm.  相似文献   

4.
In this paper, we have used the hydrogen-bonding interactions, combining the designed diamine ligands and anionic metal chlorides, into the construction of a series of new pillar-layered supramolecular complexes. The flexible molecule N,N,N′,N′-tetra-p-methoxybenzyl-ethylenediamine (L1) bearing doubly protonated H-bond donors, has been synthesized and reacted with the metal chlorides (such as [PdCl4]2?, [FeCl4]? and [CoCl4]2?) via weak C–H···Cl interactions, yielding crystal products [H2 L1]2+·Cl?·[FeCl4]? (1), 0.5H2O ? [H2 L1]2+·Cl?·0.5[PdCl4]2? (2) and [2-hydroxy naphthyl]1.5 ? 2[H2 L1]2+·2Cl?·[CoCl4]2? (3). The 3-D networks are organic double layers formed by the self-assembly of the ligands through extensive hydrogen-bonding interactions (C–H···O or C–H···π interactions) and further interconnected by [PdCl4]2?/[FeCl4]?/[CoCl4]2? in a pillar fashion, constructing into pillar-layered networks with channels accessible to various guest molecules. The inclusion property of [H2 L1][CoCl4] was studied, varieties of guest molecules, such as 2-hydroxy naphthyl, phenanthrene and hydroquinone, can be included in the framework.  相似文献   

5.
《Polyhedron》2002,21(12-13):1279-1288
The crystal structures of two mono(dpyam)copper(II) complexes, [Cu(dpyam)(NO2)2] (1) and [Cu(dpyam)(H2O)2(SO4)] (2) and two dithiocyanate compounds containing bis(dpyam)copper(II) units, [Cu(dpyam)2(NCS)](SCN)·0.5DMSO (3) and [Cu(dpyam)2(SCN)2] (4) have been determined by X-ray crystallography. The second orthorhombic form of the monomeric Cu(II) complex 1 was obtained by the reaction of di-2-pyridylamine (dpyam) with CuCl and NaNO2 in water–methanol solution. Each copper(II) ion in 1 exhibits a tetrahedrally-distorted square base of the CuN2O2 chromophore, with off-the-z-axis coordinated nitrito groups weakly bound in approximately axial positions. Complex 2 is an example of a polymeric copper(II) derivative containing the bidentate bridging sulfate ligand in the long-bonded axial positions. Each copper(II) ion in 2 shows an elongated tetragonal octahedral stereochemistry. The CuN4N′ chromophore of 3 involves a square-based pyramidal structure, slightly distorted towards a trigonal bipyramidal stereochemistry, τ=0.13. One of the SCN anions is bonded to the copper(II) ion via the N atom in the axial position of the square pyramid. Complex 4 is centrosymmetric and octahedrally elongated, with the SCN anions coordinating in axial positions via the S atom. The structures of complexes 14 and their ESR and electronic reflectance spectra are compared with those of related complexes.  相似文献   

6.
ZnII and CuII complexes of the ligand edampda2– [N,N-bis(pyridylmethyl)-ethylenediamine-N,N-diacetate] have been studied in solution by 1H n.m.r. and e.p.r. spectroscopies, respectively. [ZnII(edampda)] exists in solution in a major octahedral isomer (ca. 83%) in which the two carboxylate donors and two pyridylmethyl donors remain stereochemically rigid up to 333K at pD=6.0. The major octahedral complex has equivalent glycinato and pyridyl donors as shown by equivalent AB quartets for each type of chelate. By contrast, the [ZnII(edta)]2– analogue complex is known to have processes which rapidly equilibrate the coordinated carboxylates leading to coalesced, broad singlets instead of AB quartets down to 273K (freezing point of the sample). The minor [ZnII(edampda)] species has one pendant pyridylmethyl arm. The complex does not increase in abundance up to 333K via dissociation of the major species, suggesting that it possesses a different five-coordinate geometry (approximate trigonal bipyramid). The [CuII(edampda)] complex exhibits an e.p.r. spectrum that is intermediate between rhombic or tetragonal CuII complexes (near D4h) and the reversed-e.p.r. type of trigonal bipyramidal CuII complexes (ca. D3h). The single g value of 2.079 for gg>2.03 identifies the [CuII(edampda)] complex as distorted toward trigonal bipyramidal whereas its [CuII(edtaH2)(H2O)] analogue is known to be distorted toward square pyramidal. A binuclear CuI complex of edampda2– is formed only as a transient, and it rapidly disproportionates into [CuII(edampda)] and Cu metal. A mononuclear [CuI(edampda)]– complex persists for up to 8 h, but is oxidized within 3 min by O2 to the CuII complex. [CuII(edampda)] oxidizes to CuIII with a highly irreversible wave on glassy-carbon at +1.09V compared to the [NiII/III(edampda)] wave at +1.32V.  相似文献   

7.
Two substituted N-acylthioureas and the respective Ni(II) and Cu(II) complexes were synthesized, namely: N,N-di-n-butyl-N′-thenoylthiourea (Hnbtu); N,N-di-iso-butyl-N′-thenoylthiourea (Hibtu); bis[N,N-di-n-butyl-N′-thenoylthioureato]nickel(II), [Ni(nbtu)2]; bis[N,N-di-n-butyl-N′-thenoylthioureato]copper(II), [Cu(nbtu)2]; bis[N,N-di-iso-butyl-N′-thenoylthioureato]nickel(II), [Ni(ibtu)2]; bis[N,N-di-iso-butyl-N′-thenoylthioureato]copper(II), [Cu(ibtu)2]. The standard (p° = 0.1 MPa) molar enthalpies of formation and sublimation of the two N-acylthioureas were measured, at T = 298.15 K, by rotating-bomb combustion calorimetry and Calvet microcalorimetry, respectively. The standard (p° = 0.1 MPa) molar enthalpies of formation of the Ni(II) and Cu(II) complexes were determined, at T = 298.15 K, by high precision solution–reaction calorimetry. From the results obtained, the enthalpies of hypothetical metal–ligand and metal–metal exchange reactions, in the gaseous phase, were derived, thus allowing a discussion of the gaseous phase energetic difference between the complexation of Ni(II) and Cu(II) to 1,3-ligand systems with (S,O) ligator atoms.  相似文献   

8.
The Pd(dmen)Cl2, where dmen?=?N,N-dimethethylenediamine, was synthesized and characterized by elemental analysis and spectroscopy. The complex-formation equilibria in the reaction of [Pd(dmen)(H2O)2]2+ with 4,4′-bipiperidine (Bip) and DNA constituents were investigated at 25°C and 0.1?mol?L?1 ionic strength. The results show the formation of [(H2O)(dmen)Pd(Bip)Pd(dmen)(H2O)]4+. Inosine, uracil, and thymine interact with the previously mentioned complex by the substitution of two-coordinated water molecules. The formation constants of all possible mono- and binuclear complexes were determined and their speciation diagrams were evaluated.  相似文献   

9.
A new 1,2-diamine ligand, N,N-bis(2-hydroxyethyl)stilbenediamine (L), has been prepared by reduction of the condensation product of benzaldehyde with 2-aminoethanol with Al amalgam. Mononuclear complexes of the [CuL(H2O)]X2 type where X=Cl or AcO with CuII and PdLCl2 with palladium(II) have been prepared and characterized by elemental analysis and i.r., u.v.–vis. or 1H-n.m.r. spectroscopy.  相似文献   

10.
《Polyhedron》2001,20(22-23):2813-2821
A series of manganese-containing mononuclear and binuclear model compounds of superoxide dismutase (SOD) coordinated by a polydentate ligand N,N,N′,N′-tetrakis(2′-benzimidazolyl methyl)-1,2-ethanediamine (EDTB) have been synthesized and characterized. The SOD-like activities of these complexes have been measured by means of modified nitroblue tetrazolium (NBT) photoreduction, and the rate constants kQ of catalytic superoxide dismutation are in the range 6.96×106–2.32×107 l mol−1 s−1. In complex [Mn(EDTB)(Ac)](Ac)·C2H5OH the coordination environment around the manganese(II) ion can be described as a highly-distorted capped octahedron with an oxygen atom of the bidentate acetate ion at the capping site. This complex is the first example in which EDTB acts as a pentadentate ligand with one non-ligating benzimidazole group.  相似文献   

11.
The synthesis of the [Cu(H2L)](NO3)2 complex (I) and of a mixed-valent complex [Cu(H2L)Cl]2[CuCl2]Cl·0.5H2O (II), where L is chiral bis(menthane) propylenediaminodioxime. According to the data of single-crystal X-ray diffraction analysis, compounds I and II have ionic structures. In complex cations, the Cu2+ ion coordinates four N atoms of tetradentate chelate ligand, namely, the H2L molecule. The coordination surrounding of the Cu atom in I is a distorted square CuN4, while in II, it is a distorted square pyramid CuN4Cl. The complex anion [CuCl2]? in II has linear structure. The mutual arrangement of oxime groups in H2L corresponds to amphi-configuration of a ligand and therefore, intramolecular hydrogen bond O...H-O are formed in H2L. The complex cations in compound II are joined in dimers through hydrogen bonds Cl...H-O. The values μeff for I and II are equal to 1.82 and 2.82 μB, respectively.  相似文献   

12.
New iron(III) and cobalt(III) complexes, [Fe(2,2′-dpdtc)3], [Fe(3,3′-dpdtc)3], [Co(2,2′-dpdtc)3], and [Co(3,3′-dpdtc)3] (dpdtc?=?dipicolyldithiocarbamate) have been synthesized and their molecular structures and spectroscopic properties determined. The 2,2′- and 3,3′-dpdtc ligands have four donors, S, S′, N, and N′. These complexes are insoluble in water, but soluble in acidic solution. Crystal structures of these metal complexes reveal that the central metal ions have MS6 (M?=?Fe and Co) octahedral structures and all dipicolyl groups do not coordinate.  相似文献   

13.
Summary CuII and NiII coordination compounds with N,N,N,N-tetrakis[(2-benzimidazolyl)methyl]-1,2-cyclohexanediamine (CDTB) have been prepared and characterized. The crystal structure of [Cu(CDTB)](ClO4)2 has been determined. The geometry around the Cu atom is highly irregular and can best be described as a cis-distorted octahedron, with four short CuN bond distances of 1.988(3) Å and 2.028(3) Å, and two very long CuN bond lengths of 2.543(4) A. The cis NCuN chelate angles in the complex range from 68.8(2) for N(1)CuN(1) to 141.03° for N(4)CuN(1). The cyclic voltammogram of the complex shows a fully reversible one-electron redox wave at E 1/2 = 0.162V versus standard calomel electrode, corresponding to the CuI/II redox couple. The structure of [Ni(CDTB)](NO3)2 ·EtOH has also been determined. The geometry around the Ni atom in this compound can be described as distorted octahedral, with N(4), N(4), N(1), N(1) as the ligating atoms in the basal plane, with cis chelate angles ranging from 79.37(10) to 120.9(2)° with the trans N(2)NiN(2) angle at 175.1(2)°. The structural differences in these two compounds are undoubtedly electronic rather than steric.  相似文献   

14.
《Polyhedron》1999,18(23):3005-3012
Complexes of 2-(2′-pyridyl)quinoxaline (L) with R2SnCl2 (R=Me, Et, Bun) have been synthesized and characterized using IR, far-IR, 119Sn Mössbauer, 1H and 13C spectroscopies. The X-ray crystal structure of Et2SnCl2L shows a bidentate chelating behaviour of L, which is observed in all the diorganotin compounds presented. Interaction of the ligand L with SnCl4 resulted in the formation of a salt with the formula [(LH)2]2+[SnCl6]2−. Solution studies of the complexes R2SnCl2L (R=Me, Et, Bun) revealed partial dissociation of the ligand in chloroform.  相似文献   

15.
Summary Three novel binuclear complexes, Cr2Cl6L·EtOH, Mn2OAc4L·EtOH, Rh2Cl6L.2H2O, where L =N-hydroxyethyl-N,N,N-tribenzimidazolylmethylethylenediamine, have been prepared and characterized by elemental analyses, i.r., u.v.-vis. and e.s.r. spectra, and by magnetic susceptibility measurements. A weak antiferromagnetic spin exchange interaction exists between the metal ions in a binuclear unit for the dimanganese complex. Preliminary bioassays show that the manganese complex possesses antitumour activityin vitro.  相似文献   

16.
《Journal of Coordination Chemistry》2012,65(16-18):2569-2583
Abstract

Two copper(II) coordination complexes, formulated as [Cu(tmen)(Clba)2] (1) and [Cu(tmen)(Hsal)2·H2O] (2) (where tmen?=?N,N,N′,N′-tetramethyl ethylenediamine (C6H16N2), Clba1? = 2-chlorobenzoate (C7H4ClO21?), and Hsal1? (C7H5O31? = monoanion of o-hydroxybenzoic acid (salicylic acid)), have been synthesized and characterized by elemental combustion analysis, spectroscopic techniques, thermal studies, and single crystal X-ray analyses. Complex 1 consists of two distinct monomeric units in which the coordination environment around the central copper(II) ion is a distorted octahedron with a CuN2O4 chromophore, constituted by a chelating tmen molecule, and two 2-chlorobenzoate1? anions coordinated through their carboxylate-O atoms in an asymmetrical bidentate fashion. Complex 2 is also a monomer and consists of an CuN2O3 chromophore, in which tmen is coordinated to Cu(II) through its two N atoms in a chelating bidentate fashion, and an aqua-O and the two o-hydroxybenzoate1? (HSal1?) anions are coordinated through one of their carboxylate-O atoms in a monodentate mode, forming a square pyramidal structure. Hydrogen bonding interactions especially of O–H…O, N–H…O, and C–H…Cl types interweave monomeric units and stabilize the overall crystal structures in both complexes. Thermal analysis and antibacterial activities of 1 and 2 against various bacterial strains were also investigated.  相似文献   

17.
Thiomethylation of para-toluidine and 4(5)-methyl-2-aminothiazoles was used to synthesize N,N′-dithol-4-yl-1,3,5-thiadiazinane and N,N′-[methylene-bis-(thiomethylene)]-bis-[4(5)-methyl-1,3-thiazole-2-amines]. A fungicidal and fungistatic effect toward some microscopic fungi, plant-disease-producing factor, was revealed for these compounds.  相似文献   

18.
N,N-di-n-propyl-N′-(2-chlorobenzoyl)thiourea (HL1) (1), N,N-diphenyl-N′-(2-chlorobenzoyl)thiourea (HL2) (2), and their NiII, CoII, CuII, ZnII, PtII, CdII and PdII complexes have been synthesized and characterized. HL1 and its copper complex were characterized by single-crystal X-ray diffraction methods. The ligands coordinate as bidentates yielding essentially neutral complexes of the type [ML2]. The complexes were screened for their in vitro antibacterial, antifungal activities and toxicity. All compounds showed antimicrobial activity, but antibacterial efficacy is greater than antifungal activity.  相似文献   

19.
The synthesis and characterization of several new ruthenium complexes containing heterocyclic thiolate ligands are described. CpRu(PPh3)2Cl reacts with thiolate anions to give CpRu(PPh3)2SR, (1) [R = 2-mercaptobenzimidazolyl (a), 2-mercaptobenzothiazolyl (b), and 2-mercaptobenzoxazolyl (c)] in good yields. The CpRu(PPh3)-(CO)SR (2) complexes are obtained by treating (1) with CO gas in THF at room temperature. The one-pot reaction of CpRu(PPh3)2Cl, thiolate anions with chelate bisphosphine ligands (P–P), gave CpRu(P–P)SR where P–P = Ph2PCH2PPh2 (dppm) (3); Ph2PCH2CH2PPh2 (dppe) (4).  相似文献   

20.
Two ligands, N,N′-bis[1-(4-chlorophenyl)ethylidene]ethane-1,2-diamine (L1 ) and N,N′-bis- [1-(4-nitrophenyl)ethylidene]ethane-1,2-diamine (L2 ) and their corresponding copper(I) complexes, [Cu(L 1)2]ClO4 (1) and [Cu(L 2)2]ClO4 (2), have been synthesized and characterized by CHN analyses, 1H-NMR, IR, and UV–Vis spectroscopy. The crystal structures of L1 and [Cu(L 1)2]ClO4 (1) were determined from single crystal X-ray diffraction. L1 lies across a crystallographic inversion center and the C=N is approximately coplanar with the benzene ring and adopts E configuration. The coordination polyhedron about copper(I) in 1 is best described as a distorted tetrahedron. Quasireversible redox behavior is observed for the complexes.  相似文献   

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