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1.
A nickel(II) complex with 6-(p-chlorobenzoyl)-5,7,12,14-tetramethyl-benzo[b]-1,4,8,11- tetraazacyclo[14]tetradecine was synthesized and characterized by measurements of NMR, IR and an electronic spectra. The X-ray crystal structure shows that the coordination geometry around the Ni atom is a square planar with the unsymmetrical tetraaza[14]annulene.  相似文献   

2.
Three new complexes [Cu(L)(2)(NO(3))](NO(3))(H(2)O)(1/2)(CH(3)OH)(1/2) (1), [Cd(L)(2)(NO(3))(2)](H(2)O)(3) (2) and [Cd(L)(2)(ClO(4))(CH(3)OH)](ClO(4))(H(2)O)(1/4)(CH(3)OH) (3) (L=1-[3-(2-pyridyl)pyrazol-1-ylmethyl]naphthalene) were synthesized and characterized by elemental analyses, IR and X-ray diffraction analysis. Among them, the Cu(II) and Cd(II) ions were both coordinated by four N donors from two distinct L ligands via N,N-bidentate chelating coordination mode. Additional weak interactions, such as the face-to-face pi-pi stacking and C-Hcdots, three dots, centeredO H-bonding interactions, linked the mononuclear unit into 1D chain and further into 2D network. Complexes 1-3 were subjected to biological assays in vitro against six different cancer cell lines. All of them exhibited cytotoxic specificity and notable cancer cell inhibitory rate. The interactions of 1-3 with calf thymus DNA were investigated by thermal denaturation, viscosity measurements, spectrophotometric and electrophoresis methods. The results indicate that these complexes bound to DNA by intercalation mode via the ligand L and had different nuclease activities, which were in good agreement with their DNA-binding strength. Moreover, the central metal ions of 1-3 played a vital role in DNA-binding behaviors, DNA-cleavage activities and cytotoxicities, whereas the contribution of the different counter anions to their bioactivities also should not be ignored.  相似文献   

3.
Two new dicyanamide bridged 1D polynuclear copper(II) complexes [Cu(L1){μ1,5-N(CN)2}]n (1) [L1H = C6H5C(O)NHNC(CH3)C5H4N] and [Cu(L2){μ1,5-N(CN)2}]n (2) [L2H=C6H5C(O)CHC(CH3)NCH2CH2N(CH3)2] have been synthesised and structures of both the complexes and their crystal packing arrangements have been established by X-ray crystallography. For complex 1, a tridentate hydrazone ligand (L1H) obtained by the condensation of benzhydrazide and 2-acetylpyridine is used, whereas a tridentate Schiff base (L2H) derived from benzoylacetone and 2-dimethylaminoethylamine is employed for the preparation of complex 2. Variable temperature magnetic susceptibility measurement studies indicate there are weak antiferromagnetic interactions with J values −0.10 and −1.41 cm−1 for 1 and 2, respectively.  相似文献   

4.
The electrochemical oxidation of anodic metal (iron, cobalt, nickel and copper) in an acetonitrile solution of the potentially chelating Schiff base N,N(dithiodiethylenebis-(aminylydenemethylydene)-bis(1,2-phenylene)ditosylamide (H2L) afforded stable complexes of empirical formula [ML]. The compounds obtained have been characterized by microanalysis, IR spectroscopy and ES-MS mass spectrometry. The crystal and molecular structures of [FeL]·CH3CN (1) [CoL]·CH3CN (2), [NiL]·CH3CN (3) and [CuL]·CH3CN (4) have been determined by X-ray diffraction in all complexes, the metal atom is in a distorted tetrahedral environment with the Schiff base acting as a tetradentate N4 donor.  相似文献   

5.
Polydentate nitrogen heterocycle ligand 2,3-bis(2-pyridyl)pyrazine (2,3-dpp) reacted with M(NO3)x (M = Ag, x = 1; M = Cd, x = 2) to give two new complexes [Ag(2,3-dpp)(NO3)]2 (1) and [Cd(2,3-dpp)(NO3)2]n (2). Both complexes have been characterized by single-crystal X-ray diffraction, elemental analyses, IR and 1H NMR spectroscopy. Single-crystal X-ray analyses showed that complex 1 crystallized in monoclinic, space group P21/n is a dimmer containing penta-coordinated Ag+ ion. While compound 2 has 1D chain-like structure with repeat unit Cd(2,3-dpp)(NO3)2, in which the Cd(II) presents octa-coordinated N4O4 donor set with two four-membered chelating rings and two five-membered chelating rings around Cd(II) ion. Meanwhile, every neutral chain [Cd(2,3-dpp)(NO3)2]n is mutually connected by face-to-face π?π packing interactions to form a two dimensional layer. Furthermore, antibacterial activities of compound 1 and luminescent property of the compound 2 are also investigated.  相似文献   

6.
Pyrazole-3,5-dicarboxylate-bridged dinuclear ruthenium(II) and osmium(II) complexes of 2,2-bipyridine of composition [(bpy)2Ru(pzdc)Ru(bpy)2](ClO4) · H2O (1) and [(bpy)2Os(pzdc)Os(bpy)2](ClO4) · H2O (2) have been obtained in high yield and have been separated to their homochiral (ΛΛ/ΔΔ) rac (1a, 2a) and heterochiral (ΛΔ/ΔΛ) meso (1b, 2b) diastereoisomers. The distinctive structural features of these diastereoisomers have been characterized by 1-D and 2-D 1H NMR spectroscopy. The X-ray crystal structure of rac-[(bpy)2Os(pzdc)Os(bpy)2](ClO4) · H2O (2a) has been determined. The electrochemical and electronic spectral studies have established that there remain difference in properties and hence difference in intermetallic communication between the diastereoisomeric forms in each case.  相似文献   

7.
The cobalt(II) complexes [Co(TPA)Cl]ClO4 (1), [Co(TPA)Br]ClO4 (2), [Co(TPA)(H2O)]Cl(ClO4) (3) and [Co2(TPA)2(μ-tp)](ClO4)2 · 2H2O (4) (TPA = tris(2-methylpyridyl)amine and tp = terephthalate dianion) were synthesized and structurally characterized by UV-vis and IR spectroscopy. The molecular structures of complexes 1 and 4 were determined by X-ray crystallography and their magnetic properties were measured over the temperature range 2-300 K. The coordination geometry around the central Co(II) in these compounds has a distorted trigonal bipyamidal geometry with four nitrogen atoms from the TPA ligand and the fifth coordination site is occupied by Cl ion in 1, Br ion in 2, coordinated oxygen atom from H2O in 3 and by an oxygen atom supplied by the carboxylate group of the bridged terephthalato ligand in 4. The visible spectra of the complexes 1-3 in MeOH show strong distortion toward tetrahedral geometry. For complex 4, analysis of the infrared spectral data for the ν(COO) stretching frequencies of the tp-carboxalato groups reveals the existence of the bis(monodentate) coordination mode for the bridged tp. X-ray data for 1 and 4 show that the former is mononuclear while the latter is dinuclear. The electronic spectrum of 4 in MeOH is in complete agreement with the assigned X-ray geometry around the Co(II) centers. The magnetic behavior of the mononuclear complex 1 is indicative of a high-spin compound with zero-field splitting. The best fit was obtained with ∣D∣ = 7.3 cm−1, g = 2.25. The dinuclear complex 4 exhibits weak antiferromagnetic coupling with a coupling constant J = −0.8 cm−1. The magnetic properties and the structural parameters of 4 are discussed in relation to the other related μ-terephthalato dinuclear Co(II) compounds. The geometry of the coordination sphere around 4 is unique - the CSD compilation listing only one other compound with such a geometry around the dinuclear Co(II) complex and its composition is far different from that in 4. However, they share a common feature of having a weakly antiferromagnetic coupling between Co(II) centers.  相似文献   

8.
The reaction of Ph2PCH2CH2PPh2 (dppe) with BrCH2C(O)C6H4NO2 (1:1.05 molar ratio) in acetone produces a mixture of the new monophosphonium salt [Ph2PCH2CH2PPh2CH2C(O)C6H4NO2]Br (1) and the diphosphonium salt [NO2C6H4C(O)CH2PPh2CH2CH2PPh2CH2C(O)C6H4NO2]Br2 (2). Compound 2 was insoluble in acetone and thus easily separated from the solution of 1. Further, by reacting both the mono- and diphosphonium salts with the appropriate bases the bidentate phosphorus ylides, [Ph2PCH2CH2PPh2CHC(O)C6H4NO2] (3) and [NO2C6H4C(O)CHPPh2CH2CH2PPh2CHC(O)C6H4NO2] (4) were obtained. The reaction of ligand 3 with mercury(II) halides in dry methanol leads to the formation of the P,P-coordinated monomeric complexes {HgX2(Ph2PCH2CH2PPh2CHC(O)C6H4NO2)2} [X = Cl (5), Br (6), I (7)]. The structure of complex 7 being unequivocally determined by single crystal X-ray diffraction techniques. Characterization of these species was also performed by elemental analysis, IR spectroscopy and 1H, 31P, and 13C NMR techniques. These analyses being consistent with a 2:1 stoichiometry ylide/Hg(II) for compounds 5 through 7. Results obtained from theoretical studies are also consistent with a product in which two ylides are coordinated to the Hg(II) center through their phosphine groups, being this product the most stable among all the possible products.  相似文献   

9.
The synthesis and structural characterization of NiII, CuII and ZnII complexes of two chelating 1,2,4-oxadiazole ligands, namely 3,5-bis(2′-pyridyl)-1,2,4-oxadiazole (bipyOXA) and 3-(2′-pyridyl)5-(phenyl)-1,2,4-oxadiazole (pyOXA), is here reported. The formed hexacoordinated metal complexes are [M(bipyOXA)2(H2O)2](ClO4)2 and [M(pyOXA)2(ClO4)2], respectively (M = Ni, Cu, Zn). X-ray crystallography, 1H and 13C NMR spectroscopy and C, N, H elemental analysis data concord in attributing them an octahedral coordination geometry. The two coordinated pyOXA ligands assume a trans coplanar disposition, while the two bipyOXA ligands are not. The latter result is a possible consequence of the formation of H-bonds between the coordinated water molecules and the nitrogen atom of the pyridine in position 5 of the oxadiazole ring. The expected splitting of the d metal orbitals in an octahedral ligand field explains the observed paramagnetism of the d8 and d9 electron configuration of the nickel(II) and copper(II) complexes, respectively, as determined by the broadening of their NMR spectra.  相似文献   

10.
Synthesis of the novel ligand ferrocenyliminophosphine [(η5-C5H5)Fe{(η5-C5H4)CHN(C6H4-2-PPh2)}] (1, L) and studies on its complexation properties with mercury (II) are reported. Halogen-bridged binuclear mercury (II) complexes [HgX(μ-X)L]2 (X = Cl (2a), Br (2b)) and a mononuclear mercury (II) complex HgCl2L2 (4a) have been obtained under different reaction conditions. In both cases, the ferrocenyliminophosphine acts as a P-monodentate ligand and the imino nitrogen does not participate in coordination to mercury (II). All the new compounds 1, 2a, 2b and 4a were characterized by elemental analysis, 1H NMR, 31P NMR and IR spectra. In addition, structures of 2a and 4a have been determined by X-ray single-crystal analysis.  相似文献   

11.
Imidazolyl and 3-pyridyl are linked by azo bond (-NN-) to synthesize hitherto unknown mixed heterocyclic azo molecules, 2-[(3-pyridyl)azo]imidazole (3-PyaiH). Alkylation in presence of NaH has synthesized 1-alkyl-2-[(3-pyridyl)azo]imidazole (3-PyaiR). 3-PyaiR include three types of N-donor centers: N(imidazole), N(azo) and a peripheral N(pyridine). They bind to Ag+ to form 2:2 metallo-macrocycle, [Ag(3-PyaiR)]22+, while the reaction with Cd2+ forms Cd(3-PyaiR)42+. The complexes are structurally characterized by X-ray diffraction studies.  相似文献   

12.
Three new complexes [Pt(dpop)(Cl)2], [(Cl)2Pt(dpop)Pt(Cl)2] and [(bpy)2Ru(dpop)Pt(Cl)2](PF6)2 (dpop = dipyrido(2,3-a:3′,2′-h)phenazine) were prepared and studied. The electronic absorption spectra of the complexes display Pt dπ → dpop π* and Ru dπ → dpop π* MLCT transitions at longer wavelengths than for previously reported similar complexes. Results of cyclic voltammograms show reversible dpop centered reductions while for the mixed metal [(bpy)2Ru(dpop)Pt(Cl)2]2+ an irreversible Pt(II) oxidative wave precedes the Ru(II) oxidation/reduction couple. Spectroelectrochemical results show that all oxidative and reductive processes are completely reversible. The [(Cl)2Pt(dpop)Pt(Cl)2] complex cleaves in solution with pseudo-first order kinetics resulting in loss of the Pt dπ → dpop π* MLCT transition at 545 nm.  相似文献   

13.
Two novel Cd(II) and Zn(II) complexes with the condensation product of 2-formylpyridine and selenosemicarbazide were synthesized. The structure of Cd(II) complex was determined by X-ray crystallography. The ligand is coordinated in a neutral form via pyridine and azomethine nitrogen atoms and the selenium donor. The cadmium ion completes its five-coordination by two chloride ligands, forming a square-pyramidal geometry. The structure of Zn(II) complex was established by analysis of spectroscopic data, which indicated coordination of the ligand as a bidentate via the selenium and the azomethine nitrogen atoms. The cytotoxic activity of the newly synthesized complexes, as well as if five structurally related complexes and the ligand evaluated against eight tumor cell lines. The new Cd(II) complex showed the highest activity similar to cisplatin with IC50 less than 10 μM for all cell lines. Cell cycle distribution and apoptosis study showed that Cd(II) complex and cisplatin might have some similarity in anticancer activity, which was not the case for cisplatin and other studied complexes. Effects of the complexes on matrix metalloproteinases (MMPs) MMP-9 and MMP-2 was also studied. Cd(II) and Zn(II) complexes and cisplatin increased MMP-2 activity in supernatants of tested cells, while Ni(II) complex with the same ligand decreased the activity, implying a possible activity in preventing tumor invasion and metastasis processes.  相似文献   

14.
The crystal structure of the title compound [Fe(bpz)3](ClO4)2 · H2O (bpz=2,2-bipyrazine) has been determined by a single crystal X-ray diffraction study at 293(2) K. The complex is monoclinic, P21/c, a=17.263(3), b=9.983(2), c=17.921(4) Å, β=107.94(3)°, V=2938.3(10) Å3, Z=4, R=0.073 and Rw=0.118. The structure is made up of tris-chelated [Fe(bpz)3]2+ cations, uncoordinated perchlorate anions and crystallization water molecules. The iron atom exhibits a FeN6 distorted octahedral geometry with average Fe-N bond length and N-Fe-N bidentate angle of 1.962(5) Å and 81.6(2)°. The value of the Fe-N bond distance and that of the room temperature magnetic moment are in agreement with a singlet 1A1 ground state. The structure of 1 is compared to those of other tris-chelated iron(II) complexes with bidentate nitrogen heterocycles.  相似文献   

15.
A novel tetranuclear lanthanide(III)-copper(II) complex of macrocyclic oxamide, [Pr(CuL)3(H2O)2](SCN)3 · 1.5H2O (L = 1,4,8,11-tatraazacyclotradecanne-2,3-dione) (1), has been synthesized, structurally characterized and preliminary investigated by magnetic studies. The structure of the title complex consists of a cationic PrCu3 core, noncoordinated monovalent SCN anions and H2O molecules; the packing diagram shows open channels formed through intermolecular weak interactions. The temperature-dependent magnetic susceptibilities were analyzed by an approximate treatment being enlightened by Matsumoto et al. leading to J = −1.62 × 10−2 cm−1, Δ = 3.12 cm−1, gCu = 2.13, respectively.  相似文献   

16.
A 14-membered tetraaza macrocycle, 2,13-bis(2-carbomethoxyethyl)-5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.1.1807.12]docosane (L2) bearing two N-CH2CH2COOMe groups, and its nickel(II) and copper(II) complexes have been prepared and characterized. The nickel(II) and copper(II) complexes of 2-(2-carbomethoxyethyl)-5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.1.1807.12]docosane (L3) containing one N-CH2CH2COOMe group have also been prepared. The crystal structure of [NiL2](ClO4)2 shows that the complex has a slightly distorted trans-octahedral coordination geometry with two relatively short axial Ni-O (N-CH2CH2COOMe group) bonds (2.136(3) Å). In various solvents, however, a considerable proportion of [NiL2]2+ exists as a square-planar form, in which the functional pendant arms are not involved in coordination. The proportion of the square-planar isomer varies with solvents in the order of nitromethane ? acetonitrile < H2O < DMF ? DMSO. In the case of [CuL2](ClO4)2, only one N-CH2CH2COOMe group is involved in coordination. The N-CH2CH2COOMe group of [NiL3](ClO4)2 is not directly involved in coordination even in the solid state, though the functional group of [CuL3](ClO4)2 is coordinated to the metal ion.  相似文献   

17.
The reaction of the non-symmetric phosphorus ylides, Ph2P(CH2)nPPh2C(H)C(O)PhR [Y1-Y4: n = 1, R = Cl, Br, NO2, OCH3 and Y5-Y8: n = 2, R = Cl, Br, NO, OCH3] with dichloro(1,5-cyclooctadiene)palladium(II) in dichloromethane under mild conditions afford the monomeric P-C chelated complexes, [(Y)PdCl2] (Y = Y1-Y8). These complexes were fully characterized by elemental analysis and spectroscopic techniques such as IR, 1H, 31P, and 13C NMR. In addition, the identity of complexes [(Y5)PdCl2] (1b) and [(Y8)PdCl2] (4b) was unequivocally determined by single crystal X-diffraction techniques, both structures consisting of six-membered rings formed by coordination of the ligands through the phosphine group and the ylidic carbon atom to the metal center. The coordination geometry around the Pd atoms in both these complexes be defined as slightly distorted square planar. Furthermore, their electrochemical behavior was also investigated by cyclic voltammeters, thus the cyclic voltammetry of complex [(Y1)PdCl2], in dichloromethane solution with Pt electrode, shows that the redox reaction of the pair Pd(II)/Pd(0) is irreversible with the cathodic peak potential at −1.08 V versus Ag wire.  相似文献   

18.
Two new heptaaza Mn(II) macrocyclic bis(pendant donor) Schiff-base complexes, [MnL6]2+ and [MnL7]2+, have been prepared via Mn(II) templated [1 + 1] cyclocondensation of 2,6-diacetylpyridine with an appropriate branched hexaamine, and characterized by X-ray crystallography and spectroscopic methods. The ligands are 16- and 17-membered pentaaza macrocycles with two 2-aminoethyl pendant arms [L6 = 2,14-dimethyl-6,10-bis(2-aminoethyl)-3,6,10,13,19-pentaazabicyclo[13.3.1]nonadeca-1(19),2,13,15,17-pentaene and L7 = 2,15-dimethyl-6,11-bis(2-aminoethyl)-3,6,11,14,20-pentaazabicyclo[14.3.1]eicosa-1(20),2,14,16,18-pentaene]. The crystal structures of [MnL7]2+ and another related complex, [MnL5]2+ [L5 = 2,13-dimethyl-6,9-bis(2-aminoethyl)-3,6,9,12,18-pentaazabicyclo[12.3.1]octadeca-1(18),2,12,14,16-pentaene] were determined from X-ray diffraction data and the structure of each complex indicates that the geometry of the coordination sphere is that of a slightly distorted pentagonal bipyramid with the Mn(II) ion located within a pentaaza macrocycle and two pendant amines coordinating on opposite sides. The increased macrocycle ring size in [MnL7]2+ introduces an unusual seven-membered chelate ring and leads to long Mn-N bond lengths within the macrocycle, but to shorter pendant amine-Mn(II) bond lengths. Ab initio HF-MO calculations produce structures for the two complexes which are in close agreement with experimental findings and predict a similar structure for [MnL6]2+, but with the longest pendant amine-Mn(II) bond lengths of the three structures.  相似文献   

19.
Summary Copper(II) complexes CuL1L2 with the ligand pairs 3-phosphoglycerate (PG)/ethylenediamine (en), phosphoserine (PS)/ethylenediamine, phosphoserine/malonate (mal) are shown to be effective in inducing the release of both iron atoms from di-ferric transferrin (Fe2Tf; human serum transferrin) at pH 7.3 in 1 M NaCl at 25°C. Half-times of the reaction with Cu(PG)(en) were less than 1 min at 0.02 M concentration. The iron(III) products are polynuclear hydroxo complexes. There is weaker interaction with Cu(PS) 2 4– and virtually none with Cu(serine)(en) nor Cu(PS)(2,2-bipyridyl), revealing crucial effects of the combined ligand sphere including the phosphomonoester group. The results suggest that the release of iron from Fe2Tf, or from either monoferric transferrins, occurred due to the breakdown of the stability of iron binding in conjunction with the expulsion of the synergistic anion carbonate (or oxalate). The active copper(II) complexes are postulated to be models of membrane components that could liberate iron from transferrin succeeding its uptake at the receptor sites of cells.Abbreviations PG phosphoglycerate - PS phosphoserine - en ethylenediamine - Fe2Tf diferric transferrin - FecTf and FeNTf transferrin with iron bound to the lobe containing the C- or N-terminus, respectively - apoTf apotransferrin - K-3 all-cis-1,3,5-tris(trimethylammonio)-2,4,6-cyclo-hexanetriol - NTA nitrilotriacetic acid; bipy, 2,2-bipyridine; mal, malonate  相似文献   

20.
A new mixed-ligands metal-coordination polymer, [Cd(C4O4)(bipy)(H2O)2] (1), (bipy=4,4-bipyridine), was synthesized under hydrothermal condition and characterized by X-ray diffraction method. A three-dimensional interpenetrating network with one-dimensional channels intercalating water molecules undergoes a reversible hydration-dehydration process upon a cooling-heating cycles associated with distinct color change and structural variation.  相似文献   

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