首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 500 毫秒
1.
Two Salen-type ligands (H2L1, 4,4′-dichloro-2,2′-[(1,3-propylene)dioxybis(nitrilomethylidyne)]diphenol and H2L2, 4,4′-dinitro-2,2′-[ethylenedioxybis(nitrilomethylidyne)]diphenol) and their corresponding complexes ({[CoL1(MeOH)]2(OAc)2Co} · 2MeOH and [CuL2]2) have been synthesized and characterized by element analyses, 1H NMR, FT-IR and UV-Vis spectra, TG-DTA and single crystal X-ray crystallography. Crystallographic data suggests the octahedral geometry for Co(II) complex and square-pyramidal geometry for Cu(II) complex. Furthermore, the fluorescence behavior of Cu(II) complex in DMSO is discussed.  相似文献   

2.
《Inorganica chimica acta》1988,153(4):201-204
The reactions of the superoxide ion (O2) with tetra-p-tolyporphyrinatocobalt(II) [Co(II)TTP] in dimethyl sulfoxide(DMSO) have been investigated by use of electron spin resonance (ESR) spectroscopy. In the absence of oxygen, Co(II)TTP in DMSO gives the DMSO adduct, Co(II)(TPP)(DMSO). When this DMSO adduct is exposed to air, an oxygen complex, Co(II)(TTP)(DMSO)(O2), is formed in which the binding state between Co(II) and O2 has been considered formally as Co(III)O2. When the superoxide ion (O2 is added to this oxygen complex, a new superoxide complex, Co(II)(TTP)(O2)2, is formed. The same superoxide adduct is formed by the reaction of O2 with Co(II)TTP in the absence of oxygen.  相似文献   

3.
The tripod ligands tris(2-alkylthioethyl)amine, with alkyl = ethyl, iso-propyl, and tert-butyl, give with cobalt(II) and nickel(II) halides high-spin complexes with formulae [MLX2], [MLX]Y, and [MLX]2[MX4] (where X = Cl, Br, I; Y = BPh4, PF6). The nickel complexes are either six- or five-coordinate: the coordination number decreases as the bulkiness of the alkyl group bound to the sulfur is increased. All the cobalt complexes contain the five-coordinate cation [CoLX]+. The crystal and molecular structure of the [Co(NS3-t-Bu)Br]PF6 complex has been determined by standard X-ray methods, and refined to R = 0.061. The crystals are monoclinic, space group P21/n. The unit cell dimensions are: a = 27.420 (2), b = 11.923 (4), c = 17.082 (1) Å, β = 102.40 (1)°, Z = 8. The complex cation has a trigonal bipyramidal geometry with the nitrogen and bromine atoms at the apexes, and the three sulfur atoms in the equatorial plane. The tetrahedral distortion is relatively small (mean BrCoS angle = 98.5°), and similar to that found for the [Co (Me6tren)Br]Br complex [Me6tren = tris(2-dimethylaminoethyl)amine).  相似文献   

4.
A preparative procedure of potentially wide applicability is described for the synthesis of previously unreported tris(heteroleptic) [Cr(diimine)3]3+ complexes. The synthetic scheme involves the sequential addition of three different diimine ligands, and employs CrCl3 · 6H2O as the initial Cr(III) reagent. The synthesis and characterization of the complexes [Cr(TMP)(phen)(diimine′)]3+ are reported (where TMP = 3,4,7,8-tetramethyl-1,10-phenanthroline, phen = 1,10-phenanthroline; and diimine′ is either bpy = 2,2′-bipyridine, Me2bpy = 4,4′-dimethyl-2,2′-bipyridine, 5-Clphen = 5-chloro-1,10-phenanthroline, or DPPZ = dipyridophenazine). Chiral capillary electrophoresis and electrospray mass spectrometry were essential aids in determining the presence or absence of diimine ligand scrambling. Utilizing emission and electrochemical data obtained on these compounds, the oxidizing power of the lowest lying excited state (2Eg(Oh)) was calculated, and was found to vary in a systematic fashion with diimine ligand type.  相似文献   

5.
The syntheses and reactivity of dimethylgold(III) complexes with multidentate ligands as TRIPHOS (i.e., 1,1,1-tris(diphenylphosphinomethyl)ethane) and TREN (i.e. 2,2′,2″-triaminotriethylamine) have been examined. I.r. spectra for the compounds in the solid state, conductivity and PMR data for solutions, lead to the assignment of an ionic formula [CH3)2Au TRIPHOS]+[(CH3)2AuCl2] where the gold(III) atoms are presumably four-coordinate. The complex (CH3)2 AuCl TREN in DMSO solution undergoes a reductive elimination reaction, as found for analogous dimethylgold(III) derivatives.  相似文献   

6.
Cobalt(III) complexes with potentially tetradentate salophen (H2salophen = N,N′-bis(salicylidene)-1,2-phenylenediamine) as equatorial ligand and with different axial amine ligands (NH3, cyclohexylamine, aniline, 4-picoline and pyridine) were synthesized and characterized by IR, 1H NMR, elemental analysis. Electronic spectra and electrochemical properties of the complexes were studied in DMF solutions. The lowest energy transitions, which occur between 464.8 and 477 nm, are attributed mainly to the intraligand charge transfer, confirmed by Zindo/S electronic structure calculations. The reduction potentials of Co(III)/Co(II) are more affected than those of Co(II)/Co(I) by the axial amine ligands. The crystal structure of the [CoIII(salophen)(4- picoline)2]ClO4 · CH2Cl2 was determined, indicating that the cobalt(III) center is six coordinated surrounded by the tetradentate salophen ligand and two 4-picoline ligands. The crystal packing of the complex shows a layered structure, in which the perchlorate counter ions and also the lattice solvent molecules are intercalated between the bc planes of the complex cations.  相似文献   

7.
Prochelators are agents that have little affinity for metal ions until they undergo a chemical conversion. Three new aryl boronate prochelators are presented that are responsive to hydrogen peroxide to provide hexadentate ligands for chelating metal ions. TRENBSIM (tris[(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzylidene)-2-aminoethyl]amine), TRENBSAM (tris[(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoyl)-2-aminoethyl]amine), and TB (tris[(2-boronic acid-benzyl)2-aminoethyl]amine) convert to TRENSIM (tris[(salicylideneamino)ethyl]amine), TRENSAM (tris[(2-hydroxybenzoyl)-2-aminoethyl]amine), and TS (tris[2-hydroxybenzyl)2-aminoethyl]amine), respectively. The prochelators were characterized by 11B NMR, and the structures of TRENBSAM, TRENBSIM, and the Fe(III) complex of TS were determined by X-ray crystallography. Of the three prochelator/chelator pairs, TB/TS was identified as the most promising for biological applications, as they prevent iron and copper-induced hydroxyl radical generation in an in vitro assay. TB has negligible interactions with metal ions, whereas TS has apparent binding constants (log K′) at pH 7.4 of 15.87 for Cu(II), 9.67 Zn(II) and 14.42 for Fe(III). Up to 1 mM TB was nontoxic to retinal pigment epithelial cells, whereas 10 μM TS induced cell death. TS protected cells against H2O2-induced death, but only within a 1-10 μM range. TB, on the other hand, had a much broader window of protection, suggesting that it may be a useful agent for preventing metal-promoted oxidative damage.  相似文献   

8.
The U4+ cyclooctatetraenyl complex, [(C5Me5)(C8H8)U]2(μ-C8H8), 1, reacts with two equiv of 4,4′-dimethyl-2,2′-bipyridine (Me2bipy) and 2 equiv of 2,2′-bipyridine (bipy) to form 2 equiv of (η5-C5Me5)(η8-C8H8)U(Me2bipy-κ2N,N′) and (η5-C5Me5)(η8-C8H8)U(bipy-κ2N,N′), respectively. X-ray crystallography, infrared spectroscopy, and density functional theory calculations indicate that the products are best described as U4+ complexes of bipyridyl radical anions. Hence, only one of the (C8H8)2− ligands in 1 acts as a reductant and delivers 2 electrons per equiv of 1. Since the reduction potentials of uncomplexed (C8H8)2−, Me2bipy, and bipy are −1.86, −2.15, and −2.10 V vs SCE, respectively, it is likely that prior coordination of the bipyridine reagents enhances the electron transfer.  相似文献   

9.
Takayuki Nagasawa  Toshi Nagata 《BBA》2007,1767(6):666-670
The synthesis and electrochemistry of half-sandwich type of Co(III) complexes [(C5Me5)Co(bidentate)(CH3CN)](BF4)2 {bidentate = dppe (1,2-bis(diphenylphosphino)ethane), dppp (1,3-bis(diphenylphosphino)propane), bpy (2,2′-bipyridine), en (ethylenediamine)) are reported. Cyclic voltammograms of [(C5Me5)Co(bidentate)(CH3CN)](BF4)2 in CH3CN s showed two redox couples assignable to Co(II)/Co(III) and Co(I)/Co(II). The Co(I) complex having C5Me5 and dppe was also prepared. Two redox couples of this Co(I) complex, (C5Me5)Co(dppe), in CH3CN coincided with those of [(C5Me5)Co(dppe)(CH3CN)](BF4)2 in spite of the structural change around the metal center.  相似文献   

10.
A series of coordination polymers have been prepared by the combination of flexible ligand 1,1′-biphenyl-2,2′-dicarboxylic acid (H2dpa) and different types of nitrogen-containing ligands, with various metal ions such as Co(II), Zn(II) and Cd(II). The single-crystal structure analyses reveal that the above complexes possess different structure features with the introduction of different nitrogen-containing ligands. When auxiliary linear ligand 4,4′-bipyridine (4,4′-bpy) is introduced, two-dimensional layered complex, [Co2(dpa)2(4,4′-bpy)2(H2O)]n (1) is formed. Whereas if chelating ligand, 1,10-phenanthroline (1,10′-phen) and 2,2′-bipyridine (2,2′-bpy) are introduced, one-dimensional complex [Zn(dpa)(1,10′-phen)]n (2) and discrete complexes [Co2(dpa)2(2,2′-bpy)2(H2O)2] (3), [Co3(dpa)3(1,10′-phen)6(H2O)2] (4), [Cd(dpa)(1,10′-phen)2][(H2dpa)2(H2O)2] (5) are synthesized. To our interest, 1 and 2 crystallize in homochiral spacegroup. Furthermore, the magnetic property of complex 1 and the fluorescent properties of complexes 2 and 5 are studied.  相似文献   

11.
The new ligand hydrotris(3-(2′-furyl)-5-methylpyrazolyl)borate (TpFu,Me) was prepared by the usual procedure. With zinc salts, it forms the TpFu,MeZn-X complexes (X = Cl, Br, I, NCS, CH3COO, CF3COO). With zinc perchlorate, the bis-ligand complex Zn(TpFu,Me)2 is formed preferrably, but by carefully controlling the reaction conditions, the “enzyme model” TpFu,MeZn-OH could be obtained. The latter models carbonic anhydrase by inserting CO2 and CS2 in methanol producing TpFu,MeZn-OCOOMe and TpFu,MeZn-SCSOMe. It models hydrolases by the hydrolytic cleavage of tris(p-nitrophenyl)phosphate and γ-thiobutyrolactone. It does not hydrolyse trifluoroacetamide, but instead deprotonates it, yielding TpFu,MeZn-NHCOCF3.  相似文献   

12.
Two new Co(II) coordination polymers with mixed ligands, {[Co(BTA)0.5(DBI)2]·DBI·H2O}n (1) and [Co(PDA)(DBI)(H2O)]n (2) (H4BTA = benzene-1,2,4,5-tetracarboxylic acid; H2PDA = 2,2′-(1,2-phenylene)diacetic acid; DBI = 5,6-dimethyl-1H-benzoimidazole) have been synthesized under hydrothermal conditions, respectively. Both of them are characterized by elemental analyses, powder X-ray diffraction, thermogravimetric analysis, single-crystal X-ray diffraction, and magnetic susceptibilities. In 1, the Co(II) ions are four-coordinated and lie in distorted tetrahedron coordination environment. 1D ladder-like chain structure is formed by the bridging BTA4− ligand. In 2, the Co(II) ions are in slightly distorted octahedral coordination geometry, and linked by PDA2− ligand exhibiting a 2D layer structure. Temperature-dependent magnetic susceptibility measurements of 1 and 2 revealed that there are antiferromagnetic interactions between Co(II) ions.  相似文献   

13.
It has been established that small molecule model complexes have been useful in studying more complex biological systems of metalloproteins. Because many metalloproteins have active sites that contain multiple histidine residues bound to a metal center, a series of imidazole-containing scorpionate ligands and the associated Co and Ni complexes have been developed to investigate the bonding parameters of histidine containing active sites. The tris(2-imidazolyl) carbinol (2-TIC, 6) and tris[2-(N-methylimidazolyl)] carbinol (2-MeTIC, 7) complexes of Ni2+ and Co2+, namely [Co(2-MeTIC)2]Cl2 (8), [Co(2-MeTIC)2](NO3)2 (9), [Ni(2-MeTIC)2]Cl2 (10), [Ni(2-MeTIC)2](NO3)2 (11), [Co(2-TIC)2](NO3)2 (12), and [Ni(2-TIC)2](NO3)2 (13), have been prepared from the reaction of the appropriate ligand and appropriate metal salt in polar solvent. These complexes have been characterized by single crystal X-ray diffraction, spectroscopic techniques, and magnetic susceptibility. In each solid-state structure the metal center in the cation coordinates to three N atoms from two ligands and adopts a pseudo-octahedral coordination geometry. The X-ray characterization of tris[2-(N-methylimidazolyl)] carbinol is also reported.  相似文献   

14.
Four lead(II) complexes with substituted 2,2′-bipyridine adducts and β-diketonates ligands, [Pb(5,5′-dm-2,2′-bpy)(tfpb)2]21, [Pb(4,4′-dmo-2,2′-bpy)(tfpb)2]22, [Pb(4,4′-dm-2,2′-bpy)(tfnb)2]23 and [Pb(5,5′-dm-2,2′-bpy)(tfnb)2]24, (“4,4′-dm-2,2′-bpy”, “5,5′-dm-2,2′-bpy”, “4,4′-dmo-2,2′-bpy”, “Htfpb” and “Htfnb” are the abbreviations of 4,4′-dimethyl-2,2′-bipyridine, 5,5′-dimethyl-2,2′-bipyridine, 4,4′-dimethoxy-2,2′-bipyridine, 4,4,4-trifluoro-1-phenyl-1,3-butanedione and 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione, respectively) have been synthesized and characterized by elemental analysis, IR, 1H NMR and 13C NMR spectroscopy and also studied by thermal and electrochemical as well as X-ray crystallography. The supramolecular features in these complexes are guided/controlled by weak directional intramolecular interactions.  相似文献   

15.
Iminodiacetic acid (IDA) and tris(2‐aminoethyl)amine (TREN) chelating ligands were immobilized on poly(ethylene vinyl alcohol) (PEVA) hollow‐fiber membranes after activation with epichlorohydrin or butanediol diglycidyl ether (bisoxirane). The affinity membranes complexed with Cu(II) were evaluated for adsorption of human immunoglobulin G (IgG). The effects of matrix activation and buffer system on adsorption of IgG were studied. Isotherms of batch IgG adsorption onto finely cut membranes showed that neither of the chelates, IDA‐Cu(II) or TREN‐Cu(II), had a Langmuirean behavior with negative cooperativity for IgG binding. A comparison of equilibrium and dynamic maximum capacities showed that the dynamic capacity for a mini‐cartridge in a cross‐flow filtration mode (52.5 and 298.4 mg g?1 dry weight for PEVA‐TREN‐Cu(II) and PEVA‐IDA‐Cu(II), respectively) was somewhat higher than the equilibrium capacity (9.2 and 73.3 mg g?1 dry weight for PEVA‐TREN‐Cu(II) and PEVA‐IDA‐Cu(II), respectively). When mini‐cartridges were used, the dynamic adsorption capacity of IDA‐Cu(II) was the same for both mini‐cartridge and agarose gel. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

16.
Two new binuclear copper complexes, [Cu2(oxpn)(bpy)(pic)(H2O)](pic) (1) and [Cu2(oxpn)(Me2bpy)(pic)](pic) (2) [H2oxpn = N,N′-bis(3-aminopropyl)oxamide; Hpic = 2,4,6-trinitrophenol; bpy = 2,2′-bipyridine; Me2bpy = 4,4′-dimethyl-2,2′-bipyridine], have been synthesized and characterized by elemental analyses, conductivity measurements, IR, UV-visible spectroscopy and single crystal X-ray analyses. Both complexes have similar molecular structures. In complex 1, the central two Cu(II) atoms are bridged by cis-oxpn2− with the Cu1-Cu2 separation of 5.221 Å and the polyhedron of each copper atom is a square-pyramid. Similarly, complex 2 is a cis-oxpn2−-bridged binuclear complex with the Cu1-Cu2 separation of 5.196 Å. Cu1(II) central atom situated in a tetrahedral geometry is four-coordinated and Cu(II) atom situated in a square-pyramidal geometry is five-coordinated. Hydrogen bonding interactions and π-π stacking interactions link the binuclear copper complex 1 or 2 into a 2D infinite network. The antibacterial assays indicate that the two complexes showed better activities than their ligands. The interactions of the two binuclear complexes with herring sperm DNA (HS-DNA) have been studied by UV absorption titration, fluorescence titration and viscosity measurements. The results suggest that the two binuclear complexes bind to HS-DNA via an intercalative mode.  相似文献   

17.
The crystal structures of several Pt(II) complexes containing sulfoxide ligands are described. The two iodo bridged dimers of the type I(R2SO)Pt(μ-I)2Pt(R2SO)I (where R is ethyl or n-butyl) are twinned structures. The dinuclear species are the trans isomers. Two compounds of the type trans-Pt(DMSO)(amine)X2 were studied by X-ray diffraction methods. The diiodo MeNH2 compound forms H-bonded chains, formed by maximizing the H-bonds between the amine group with the O atom of DMSO and one iodo ligand. The H-bonding pattern is quite different in the dichloro t-BuNH2 complex. In the latter crystal, there are two independent molecules which are H-bonded in pairs. The methyl groups of DMSO and the t-butyl group of the amine are oriented towards the outside of the pairs of molecules, while the H-bonds link the two independent molecules. Again, the amino group forms the maximum H-bonds with the O atom of DMSO and one chloro ligand. The crystal structures of trans-Pt(DMSO)(pyridine)I2 and of trans-Pt(MeBzSO)(pyrimidine)I2 (Bz = benzyl) were also studied. In the pyridine complex, the O atom of DMSO is in the Pt(II) plane by symmetry, while in the pyrimidine compound, the C atom of the –CH3 group is in the Pt(II) plane. The pyridine and the pyrimidine ligands are perpendicular to the Pt(II) square plane. The trans influence of the different ligands is discussed.  相似文献   

18.
The nickel(II) complexes with the quinolone antibacterial agents oxolinic acid, flumequine, enrofloxacin and sparfloxacin in the presence of the N,N′-donor heterocyclic ligand 2,2′-bipyridylamine have been synthesized and characterized. The quinolones act as bidentate ligands coordinated to Ni(II) ion through the pyridone oxygen and a carboxylato oxygen. The crystal structure of [(2,2′-bipyridylamine)bis(sparfloxacinato)nickel(II)] has been determined by X-ray crystallography. UV study of the interaction of the complexes with calf-thymus DNA (CT DNA) has shown that they bind to CT DNA with [(2,2′-bipyridylamine)bis(flumequinato)nickel(II)] exhibiting the highest binding constant to CT DNA. The cyclic voltammograms of the complexes have shown that in the presence of CT DNA the complexes can bind to CT DNA by the intercalative binding mode which has also been verified by DNA solution viscosity measurements. Competitive study with ethidium bromide (EB) has shown that the complexes can displace the DNA-bound EB indicating that they bind to DNA in strong competition with EB. The complexes exhibit good binding propensity to human or bovine serum albumin protein having relatively high binding constant values. The biological properties of the [Ni(quinolonato)2(2,2′-bipyridylamine)] complexes have been evaluated in comparison to the previously reported Ni(II) quinolone complexes [Ni(quinolonato)2(H2O)2], [Ni(quinolonato)2(2,2′-bipyridine)] and [Ni(quinolonato)2(1,10-phenanthroline)]. The quinolones and their Ni(II) complexes have been tested for their antioxidant and free radical scavenging activity. They have been also tested in vitro for their inhibitory activity against soybean lipoxygenase.  相似文献   

19.
A series of water soluble complexes of general formula [(η6-arene)Ru{(C5H4N)2CNRi}Cl]PF6 have been prepared by the reaction of [{(η6-arene)RuCl2}2] with appropriate 2,2′-dipyridyl-N-alkylimine ligands (dpNRi) in the presence of NH4PF6 (where; R = Me or Et; arene = p-cymene, C6Me6, C6H6). The 2,2′-dipyridyl-N-alkylimine ligands are prepared by reaction of 2,2′-dipyridyl ketone with the corresponding alkylamine. The complexes are readily obtained as air stable yellow to dark brown solids by simple stirring at room temperature. The complexes are isolated as their hexafluorophosphate salts and characterized on the basis of spectroscopic data. The molecular structure of representative complex [(η6-C6Me6)Ru{(C5H4N)2CN-Me}Cl]PF6 has been determined by single crystal X-ray diffraction studies.  相似文献   

20.
Novel N-N-N-O-type of tetradentate ligands H3obap (H3obap = oxamido-N-aminopropyl-N′-benzoic acid) and H3maeb (H3maeb = malamido-N-aminoethyl-N′-benzoic acid) and the corresponding square-planar copper(II) complexes have been prepared and characterized. The obap3− and maeb3− ligands coordinate to the copper(II) ion via four ligating atoms (three deprotonated atoms: one carboxylate oxygen and two deprotonated amide nitrogens; one amine nitrogen) with in-plane square chelation. A four coordinate, square-planar geometry has been established crystallographically for the binuclear Na2[Cu(obap)]2 · 2H2O complex. Structural data correlating the square-planar geometry of the [Cu(obap)] unit and an extensive strain analysis are discussed in relation to the information obtained for similar complexes. The infrared and electronic absorption spectra of the complexes are discussed in comparison to the related complexes of known geometries. Antibacterial activity of ligands and copper(II) complexes towards common Gram-negative and Gram-positive bacteria are reported as well.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号