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1.
A novel ligand, N,N′‐Bis‐[3‐(2‐nitrophenyl)‐allylidene]‐ethane‐1,2‐diamine (nca2en), and their corresponding copper(I) complexes, [Cu(ncaen)2]ClO4 ( 1 ), and [Cu(nca2en)(PPh3)2]BPh4 ( 2 ), have been synthesized and characterized by CHN analyses, 1H and 13C‐NMR, IR, and UV‐Vis spectroscopy. The crystal and molecular structures of [Cu(ncaen)2]ClO4 ( 1 ), and [Cu(nca2en)(PPh3)2]BPh4 ( 2 ), were determined by X‐ray crystallography from single‐crystal data. The coordination polyhedron about the copper(I) atom in the two complexes is best described as a distorted tetrahedron. A quasireversible redox behavior is observed for complex 1 and 2 (E1/2 = 0.55 and 0.95 V, respectively).  相似文献   

2.
New mixed-ligand copper(I) complexes, [Cu(Phca2en)(PPh3)X], [Phca2en = N,N′-bis(β-phenylci-nnamaldehyde)-1,2-diiminoethane and X=Cl (1), Br (2), I (3), NCS (4), N3 (5)] have been synthesized and characterized by various techniques. 1H and 13C-NMR and IR spectral data of these copper(I) complexes are compared with the free ligand to elucidate some structural features. The structures of [Cu(Phca2en)(PPh3)Br] (2) and [Cu(Phca2en)(PPh3)I] (3) have been determined from single-crystal data showing that the coordination geometry around copper atom is a distorted tetrahedron. Furthermore, these Cu(I) complexes exhibit supramolecular motifs of the type multiple phenyl embraces resulting from attractive interactions between phenyl rings of PPh3 moieties. The presence of the C–H…Cu weak intramolecular hydrogen bonds, due to the trapping of C–H bonds in the vicinity of the metal atoms, is also reported.  相似文献   

3.
Two copper(I) complexes [Cu(Cin2bda)2]ClO4 (I) and [Cu(Ncin2bda)2]ClO4 (II) have been prepared by the reaction of the ligands N2,N2′-bis(3-phenylallylidene)biphenyl-2,2′-diamine (L1) and N2,N2′-bis[3-(2-nitrophenyl)allylidene]biphenyl-2,2′-diamine (L2) and copper(I) salt. These compounds were characterized by CHN analyses, 1H NMR, IR, and UV-Vis spectroscopy. The C=N stretching frequency in the copper(I) complexes shows a shift to a lower frequency relative to the free ligand due to the coordination of the nitrogen atoms. The crystal and molecular structure of II was determined by X-ray single-crystal crystallography. The coordination polyhedron about the copper(I) center in the complex is best described as a distorted tetrahedron. A quasireversible redox behavior was observed for complexes I and II. The article is published in the original.  相似文献   

4.
Synthesis, spectroscopy, and crystal structures of [Cu(ca2en)2]ClO4 ( 1 ) and [Cu(ca2en)(PPh3)2]ClO4 ( 2 ) (ca2en=N,N′‐bis(trans‐cinnamaldehyde)ethylenediimine) are reported. Compound 1 crystallizes in the orthorhombic space group Pbca, with a=12.5647(7), b=21.8203(11), c=27.992(2) Å, V=7674.3(7) Å3, Z=8. Compound 2 crystallizes in the triclinic space group P , with a=13.0540(11), b=14.2935(13), c=14.9863(13) Å, α=84.130(2), β=69.761(2), γ=87.749(2)°, V=2609.8(4) Å3, Z=2. The coordination polyhedron about the CuI center in the two complexes is best described as a distorted tetrahedron. The 1H‐NMR and electronic spectra of these complexes are also reported and discussed. The cyclic voltammetry of the complexes indicate a quasireversible redox behavior for complex 1 (E1/2=0.51 V). However, complex 2 displays an irreversible oxidation wave at 0.91 V. A weak emission is observed for complex 2 in CHCl3 at room temperature.  相似文献   

5.
Li  Baolong  Xu  Zheng  Cao  Zhengbai  Zhu  Liming  Yu  Kaibei 《Transition Metal Chemistry》1999,24(6):622-627
The reaction of diethylenetriamine (dien) and 1,2-bis(1,2,4-triazole-1-yl)ethane (btrz) with Cu(ClO4) · 6H2O forms [Cu(dien)(btrz)(ClO4)2] (1), and the reaction of [Cu(en)2(ClO4)2] (en = ethylenediamine) with btrz forms [Cu(en)2(btrz)(ClO4)2] (2). Complexes (1) and (2) were characterized by elemental analysis, i.r., electronic spectroscopy, e.s.r. and magnetic susceptibility. Their crystal structure was determined by X-ray diffraction. In complex (1), Cu is coordinated by a dien and two btrz, forming a distorted CuN5 square pyramid with one btrz bound at the apical position. In complex (2), Cu is coordinated by two en and two nitrogen atoms of btrz forming an elongated octahedron. Both complexes have a one-dimensional chain structure in which btrz ligands bridge between pairs of Cu atom.  相似文献   

6.
The title compound, bis[di­aqua­bis­(ethyl­enedi­amine‐κ2N,N′)copper(II)­] hexa­cyano­iron(II) tetrahydrate, [Cu(C2H8N2)2(H2O)1.935]2[Fe(CN)6]·4H2O, was crystallized from an aqueous reaction mixture initially containing CuSO4, K3[Fe(CN)6] and ethyl­enedi­amine (en) in a 3:2:6 molar ratio. Its structure is ionic and is built up of two crystallographically different cations, viz. [Cu(en)2(H2O)2]2+ and [Cu(en)2(H2O)1.87]2+, there being a deficiency of aqua ligands in the latter, [Fe(CN)6]4− anions and disordered solvent water mol­ecules. All the metal atoms lie on centres of inversion. The Cu atom is octahedrally coordinated by two chelate‐bonded en mol­ecules [mean Cu—N = 2.016 (2) Å] in the equatorial plane, and by axial aqua ligands, showing very long distances due to the Jahn–Teller effect [mean Cu—O = 2.611 (2) Å]. In one of the cations, significant underoccupation of the O‐atom site is observed, correlated with the appearance of a non‐coordinated water mol­ecule. This is interpreted as the partial contribution of a hydrate isomer. The [Fe(CN)6]4− anions form quite regular octahedra, with a mean Fe—C distance of 1.913 (2) Å. The dominant intermolecular interactions are cation–anion O—H⋯N hydrogen bonds and these inter­actions form layers parallel to (001).  相似文献   

7.
The mononuclear palladium(II) complex trans-[PdCl2(PhPPy2)2] (1) reacts with [Cu(CH3CN)4]ClO4 to afford the heterobinuclear [(PhPPy2)2PdCuCl2]ClO4·2CH3CN (2), bridged by two PhPPy2 ligands in a new mode. Complex 2 crystallizes in space group P21/c with a?=?12.947(1), b?=?9.142(1), c?=?33.454(2)?Å, β?=?99.698(1)°. The copper(I) and palladium(II) ions in 2 adopt distorted tetrahedral and square-planar geometry, respectively. At room temperature, the complex is photoluminescent in solution.  相似文献   

8.

Reaction of the ligand 3-(pyridin-2-yl)pyrazole (L) with Cu(ClO4)2 and CuX2 (X=Cl, Br, I) gives complexes with stoichiometry [Cu(L)2X]ClO4 (X = Cl, Br, I). The new complexes were characterized by elemental analyses and infrared and electronic spectroscopy. The crystal structure of the [Cu(L)2Br]ClO4 was determined by X-ray crystallography. The cation complex (i.e. [Cu(L)2Br]P) contains copper(II) with a distorted trigonal bipyramid geometry with a Br ligand occupying an equatorial site. The penta-coordinated metal atom is bonded to two pyridinic nitrogens, two pyrazolic nitrogens, and one bromide anion. The pyrazolic H atoms are hydrogen bonded to Br atoms, resulting in infinite hydrogen-bonded chains running in the b direction. There are π‐π stacking interactions (charge-transfer arrays) between the parallel aromatic rings belonging to adjacent chains that may help to form hydrogen bonding in the coordination geometry around Cu (II).  相似文献   

9.
Partial reduction of the CuII ions in the aqueous system CuII–en–[Ni(CN)4]2? (1/1/1) (en is 1,2‐di­amino­ethane) yields a novel heterobimetallic mixed‐valence compound, poly­[[aqua­bis(1,2‐di­amino­ethane)copper(II)] [hexa‐μ‐cyano‐tetra­cyano­bis(1,2‐di­amino­ethane)­tricopper(I,II)­dinickel(II)] dihydrate], [Cu(C2H8N2)2(H2O)][Ni2Cu3(CN)10(C2H8N2)2]·2H2O or [Cu(en)2(H2O)][Cu(en)2Ni2Cu2(CN)10]·2H2O. The structure is formed by a negatively charged two‐dimensional array of the cyano complex [Cu(en)2Ni2Cu2(CN)10]n2n?, [Cu(en)2(H2O)]2+ complex cations and water mol­ecules of crystallization. These last are involved in a complicated hydrogen‐bonding system. The cyano groups act as terminal, μ2‐bridging or μ3‐bridging ligands.  相似文献   

10.
《Polyhedron》2001,20(7-8):695-702
Three Co(III) complexes of the type [Co(salophen)(amine)2]ClO4, salophen=N,N′-disalicylidene-1,2-phenylendiamine dianion and amine=morpholine (1), pyrrolidine (2), and piperidine (3), have been synthesized and characterized by elemental analysis, IR, UV–Vis, 1H, and 13C NMR spectroscopy. [Co(salophen)(morpholine)2]ClO4 (1) and [Co(salophen)(pyrrolidine)2]ClO4 (2) have been studied by X-ray diffraction. Compound 1 crystallizes in ribbons of complexes and perchlorates held together by weak NH⋯O and CH⋯O hydrogen bonds between morpholines and perchlorates. The latter also interconnect the chains to a 3D network. Some minor π–π interactions exist. Compound 2 crystallizes as endless chains of complexes linked by weak CH⋯O hydrogen bonds to the disordered perchlorates. The pyrrolidine moiety is turned by 90° with respect to 1 and forms intramolecular NH⋯O hydrogen bonds. The coordination polyhedra of 1 and 2 possess Cs symmetry, and the salophens are not planar in either of them.  相似文献   

11.
Halomercurates: Syntheses and Crystal Structures of [Cu(en)2][Hg2Cl6], [Cu(en)2][Hg2Br6], and [Cu(en)2][HgBr4] Crystals of [Cu(en)2][Hg2Cl6] ( 1 ) have been obtained by layering a solution of Hg(NO3)2 and NaCl with a solution of [Cu(en)2]SO4. An analogous procedure, using NaBr instead of NaCl, gave crystals of [Cu(en)2][HgBr4] ( 3 ). Crystals of [Cu(en)2][Hg2Br6] ( 2 ) were obtained by gel crystallization using the same starting materials as for 3 . The complexes show very low solubility. The dinuclear anions of 1 consist of two nearly planar HgCl3 units related by a center of symmetry. In 2 infinite anionic chains are present, made up of parallel HgBr3 units. These units are packed in such a way as to produce a trigonal bipyramidal configuration around the Hg atoms. 3 contains mononuclear deformed tetrahedral [HgBr4]2– anions. In all three complexes the packing of the ions is such that halogen atoms of halomercurate anions complete a tetragonal bipyramidal coordination at Cu. The resulting Cu–Halogen distances are 2.924 Å for 1 , 3.036 Å for 2 and 3.085 and 3.119 Å for 3 . 1 : Space group P 1, Z = 1, lattice constants at 20 °C: a = 7.000(2), b = 7.526(2), c = 8.239(2) Å; α = 88.39(2), β = 86.06(2), γ = 86.10(3)°; R1 = 0.040. 2 : Space group P21/c, Z = 2, lattice constants at –50 °C: a = 7.185(1), b = 16.338(2), c = 7.814(1) Å; β = 94.88(2)°; R1 = 0.033. 3 : Space group P21/n, Z = 4, lattice constants at 20 °C: a = 8.055(3), b = 13.101(3), c = 13.814(3) Å; β = 91.24(3)°; R1 = 0.092.  相似文献   

12.
From the 1:1 system of [Cu(dien)2](NO3)2 and K[Ag(CN)2] in water (dien is diethyl­enetri­amine, C4H13N3), the novel compound catena‐poly­[bis­[[μ‐cyano‐1:2κ2C:N‐diethyl­enetri­amine‐2κ3N‐copper(II)silver(I)]‐μ‐cyano‐1:2′κ2C:N] di­cyano­silver(I) tri­cyanodisilver(I)], [CuAg(CN)2(dien)]2[Ag(CN)2][Ag2(CN)3], has been isolated. The structure is formed from positively charged [–Cu(dien)–NC–Ag–CN–]nn+ chains and two isolated centrosymmetric [Ag(CN)2]? and [Ag2(CN)3]? anions. In the cationic chains, the Cu atoms are linked by bridging di­cyano­argentate groups, and the deformed square‐pyramidal coordination polyhedron of the CuII cation is formed from a tridentate chelate‐like bonded dien ligand and two N‐bonded bridging cyano groups. One of the bridging cyano groups occupies the apical (ap) position [mean Cu—­Neq = 2.02 (2) Å, and Cu—Nap = 2.170 (3) Å; eq is equatorial]. Short argentophilic interactions in the range 3.16–­3.30 Å are present in the crystal structure.  相似文献   

13.
Novel copper(II) X-salicylate complexes with N,N-diethylnicotinamide (dena) of the formula [Cu(RCOO)2(dena)2(H2O)2] (RCOO = 3-methylsalicylate anion (3-Mesal, 1), 4-methylsalicylate anion (4-Mesal, 2), 5-methylsalicylate anion (5-Mesal, 3), 5-methoxysalicylate anion (5-MeOsal, 4) or 4-methoxysalicylate anion (4-MeOsal, 5)), and complex [Cu(3-MeOsal)2(dena)2(H2O)2]∙2H2O (3-MeOsal = 3-methoxysalicylate anion (6)) have been prepared in the crystalline forms and characterized by spectroscopic methods (IR, Vis–UV, EPR). All the compounds according to their composition (15) seem to possess octahedral copper(II) stereochemistry. The complex 1 has been prepared in two different forms. X-ray analyses of the complexes 1, 4, and 5 were carried out and they featured a tetragonal-bipyramidal geometry around the copper atoms. The tetragonal planes are created by X-salicylate anions bonded to the copper(II) atoms via unidentate carboxylate oxygen atoms and the pyridine ring nitrogen atoms of the neutral ligand N,N-diethylnicotinamide, while in axial positions are water molecules. The two forms of complex 1 present conformation polymorphs and supramolecular isomers.  相似文献   

14.
Trans-[Cr(en)2F2]ClO4 (en = 1,2-diaminoethane) has triclinic P1 space group with a = 5.633(1), b = 8.879(2), c = 11.686(2) Å, α = 99.92(2), β = 87.22(2), γ = 100.02(2)° and Z = 2. The unit cell contains two independent trans-Cr(en)2F2+ cations and ClO4? anion. Average Cr? F bond length is 1.88(1) Å. Cr? N bonding distances are from 2.05 to 2.10 Å. Mean Cl? O distance is 1.36 Å. 1,2-diaminoethans are in the gauche conformation. Trans-[Cr(en)2F2]Cl and [Cr(en)2F2]Br have monoclinic and orthorhombic space groups with four equivalent Cr(en)2F2+ cations. Trans-[Cr(en)2F2]I forms twinned crystals preventing further crystallographic investigation.  相似文献   

15.
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   

16.
Four copper(II) complexes and one copper(I) complex with pyridine-containing pyridylalkylamide ligands N-(pyridin-2-ylmethyl)pyrazine-2-carboxamide (HLpz) and N-(2-(pyridin-2-yl)ethyl)pyrazine-2-carboxamide (HLpz?) were synthesized and characterized. The X-ray crystal structures of [Cu2(Lpz)2(4,4?-bipy)(OTf)2] (1, OTf?=?trifluoromethanesulfonate, 4,4?-bipy?=?4,4?-bipyridine) and [Cu(Lpz)(py)2]OTf·H2O (2, py?=?pyridine) revealed binuclear and mononuclear molecular species, respectively, while [Cu(Lpz)(μ2-1,1-N3)]n (3), [Cu(Lpz?)(μ2-1,3-N3)]n (4), and [Cu(HLpz)Cl]n (5) are coordination polymer 1-D chains in the solid state.  相似文献   

17.
A new complex, [Cu(imme2py)2](ClO4) (imme2py?=?2-(2′-(6′-methylpyridyl))-4,4,5,5-tetramethyl-1H-imidazolyl-1-oxyl) has been synthesized and structurally characterized by X-ray diffraction methods. It crystallizes in the orthorhombic crystal system, space group P 212121 . The structure consists of [Cu(imme2py)2]+ cations and chloride anions. The coordination geometry about Cu(I) is tetrahedral with the four coordination sites being occupied by four nitrogen atoms. Magnetic measurements show intramolecular antiferromagnetic interactions between the imino nitroxides.  相似文献   

18.
Copper(I) complexes of thioureas having the general formulae [CuLnBr] and [CuLn]Br [where, n = 1 − 4 and L = thiourea (Tu), N-methylthiourea (Metu), N-ethylthiourea (Ettu), N,N-dipropylthiourea (Dprtu), N,N-dibutylthiourea (Dbtu) or N,N-diphenylthiourea (Dphtu)] were prepared and characterized by elemental analysis, IR, and NMR (1H and 13C) spectroscopy. The crystal structure of one of them, [Cu(Metu)4]Br (1), was determined by X-ray crystallography. The X-ray structure of 1 describes a tetrahedral geometry around copper(I) with all Metu ligands binding through sulfur atoms. An upfield shift in the 13C NMR and downfield shift in the 1H NMR spectra are consistent with the thione coordination to copper(I). Antimicrobial activities of the complexes were evaluated by the minimum inhibitory concentration method. The results showed that only [Cu(Ettu)3Br] was effective in inhibiting the growth of all the tested organisms (gram-positive, gram-negative bacteria, and Candida sp.), while the other complexes were not effective against all the organisms.  相似文献   

19.
The first tetranuclear nickel complex with the oxamato ligand, {[Ni(en)2]4[H4L]}(ClO4)4·7H2O ( 1 ) (L = N, N′, N″, N‴-methanetetrayltetrakismethylenetetrakis (oxamato)), has been prepared and determined by single-crystal X-ray analysis. 1 crystallizes in the tetragonal space group I41/a, with a = 15.2744(9), c = 31.3748(2) Å and Z = 4. Each nickel (II) ion is in a distorted octahedral donor atom environment, which comprises four nitrogen atoms of two en molecules and two oxygen atoms of oxamato bridge. The shape of the entity looks like a propeller. The temperature-dependent magnetic susceptibilities were analyzed by the Curie-Weiss law; the following values were found C = 4.36 cm3 K mol-1, θ = -24.7 K, respectively.  相似文献   

20.
Two new salts of the cation [CuI(dmp)2]+ (dmp is 2,9‐dimeth­yl‐1,10‐phenanthroline, C14H12N2), namely bis­[bis­(2,9‐dimeth­yl‐1,10‐phenanthroline‐κ2N,N′)copper(I)] bis­(hexa­fluorophos­phate) hemi[bis­(4‐pyridylmethyl­idene)hydrazine] acetonitrile solvate, [Cu(C14H12N2)2]2(PF6)2·0.5C12H10N4·C2H3N or [Cu(dmp)2]2(PF6)2·0.5(bpmh)·CH3CN [bpmh is bis­(4‐pyridylmethyl­idene)hydrazine, C12H10N4], (I), and bis­(2,9‐dimeth­yl‐1,10‐phenanthroline‐κ2N,N′)copper(I) dicyanamide, [Cu(C14H12N2)2](C2N3) or [Cu(dmp)2][N(CN)2], (II), are reported. The Cu—N bond lengths and the distortion from idealized tetra­hedral geometry of the dmp ligands are discussed and compared with related compounds. The bpmh molecule in (I) is π–π stacked with a dmp ligand at a distance of 3.4 Å, rather than coordinated to the metal atom. The molecule lies across an inversion center in the crystal. In (II), the normally coordinated dicyanamide mol­ecule is present as an uncoordinated counter‐ion.  相似文献   

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