Two homochiral mercury (1) and cadmium (2) complexes derived from chiral twisted biphenyl pyridine ligand (3,3'-bipyridine-5,5',6,6'-tetramethyl-2,2'-dimethoxy-1,1'-biphenyl) have been synthesized and chara...Two homochiral mercury (1) and cadmium (2) complexes derived from chiral twisted biphenyl pyridine ligand (3,3'-bipyridine-5,5',6,6'-tetramethyl-2,2'-dimethoxy-1,1'-biphenyl) have been synthesized and characterized by IR, microanalysis, TGA, UV-Vis, powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P21212 with Z = 2. For 1, a = 14.2038(16), b = 14.3630(17), c = 7.0257(8), V = 1433.3(3)3, Mr = 878.91, Dc = 2.037 g/cm3, μ = 7.549 mm-1, F(000) = 824, the final GOF = 1.017, R = 0.0296 and wR = 0.0645 for 2925 observed reflections with I 2σ(I). For 2, a = 14.212(3), b = 14.392(3), c = 7.0498(14), V = 1442.0(5)3, Mr = 790.72, Dc = 1.821 g/cm3, μ = 2.924 mm–1, F(000) = 760, the final GOF = 1.075, R = 0.0340 and wR = 0.0834 for 3144 observed reflections with I 2σ(I). The crystal structures of 1 and 2 are isostructural and each adopts a two-dimensional supramolecular network which contains the C–H···π interactions.展开更多
Novel polymeric Cu<sup>2+</sup> complexes derived from the reaction of cyanoacetylhydrazine (<strong>CAH</strong>;<strong>L</strong>) with CuCl<sub>2</sub>•2H<sub>...Novel polymeric Cu<sup>2+</sup> complexes derived from the reaction of cyanoacetylhydrazine (<strong>CAH</strong>;<strong>L</strong>) with CuCl<sub>2</sub>•2H<sub>2</sub>O in different solvents were synthesized and characterized. The isolated solid polymeric complexes were investigated using modern conventional physicochemical and spectral (IR, <sup>1</sup>H-NMR, UV-Vis. ESR, Raman), magnetic and thermal studies. The results revealed that <strong>CAH</strong> behaves in different ways towards the coordination of the Cu<sup>2+</sup> ion. The promotion of solvents to the cyano group was discussed on the basis of the solvent and the Cu<sup>2+</sup> ion used. Magnetic and spectral studies suggest octahedral geometry is proposed for the Cu<sup>2+</sup> complexes. EPR studies indicate the existence of polymeric complexes depending on the results of <i>g</i>-values. The results suggest that the number of copper atoms ranges from three to twelve atoms. The molecular modeling is drawn and some chemical characteristics are calculated such as chemical reactivity and energy components are investigated between the different types of the ligands.展开更多
The ternary complexes containing Cu(II),L-His and nucleotide (5'-GMP and 5'-IMP)were synthesized and characterized.IR and ~1H NMR spectra show that Cu(II)binds to carboxylate oxygen and imidazole nitrogen of L...The ternary complexes containing Cu(II),L-His and nucleotide (5'-GMP and 5'-IMP)were synthesized and characterized.IR and ~1H NMR spectra show that Cu(II)binds to carboxylate oxygen and imidazole nitrogen of L-His and purine N_7 of 5'-GMP and 5'-IMP.The interaction of Cu(II)with Po_3^(2-)of 5'-GMP is present,but that for 5'-IMP is not present.展开更多
The synthesis and structural characterization of cobalt(II) complexes of amino acid Schiff bases was prepared from Salicylaldehyde and three amino acid (Valine, Leucine, and Isoleucine)?in basic medium. The metal comp...The synthesis and structural characterization of cobalt(II) complexes of amino acid Schiff bases was prepared from Salicylaldehyde and three amino acid (Valine, Leucine, and Isoleucine)?in basic medium. The metal complexes was synthesized by treating an ethanolic solution of the ligand with appropriate amount of metal salts [1:2] [M:L] ratio. The synthesized Schiff bases and their metal complexes have been investigated on the bases of elemental chemical analysis, FTIR, electronic spectral,?1HNMR,?13CNMR, MS, molar conductance and magnetic susceptibility measurements. The electronic spectra of the metal complexes and their magnetic susceptibility measurements suggest octahedral structures are the probable coordination geometries for the isolated complexes. The Schiff bases and their metal complexes were preliminary scanned against various strains of microbes to study their biological effect.展开更多
Using two new flexible and functional nitronyl nitroxide radicals as ligands, two copper (II) complexes {[Cu(hfac)<sub>2</sub>]<sub>3</sub>(NITmPhO3Py)<sub>2</sub>}<sub>n...Using two new flexible and functional nitronyl nitroxide radicals as ligands, two copper (II) complexes {[Cu(hfac)<sub>2</sub>]<sub>3</sub>(NITmPhO3Py)<sub>2</sub>}<sub>n</sub> (1) and [Cu(hfac)<sub>2</sub><sub> </sub>(NIToPhO3Py)]<sub>2</sub> (2) (NITmPhO3Py = 2-[(3-methoxy-pyridinyl)phen-3-yl]- 4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, NIToPhO3Py = 2-[(3-methoxy-pyridinyl)phen-2-ly]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, hfac = hexafluoroacetylacetone), have been characterized structurally and magnetically. The X-ray crystal analyses showed that complex 1 displayed a chain polymer structure which formed with {[Cu(hfac)<sub>2</sub>]<sub>3</sub>(NITmPhO3Py)<sub>2</sub>}<sub>n</sub> due to the cross-linking of two cyclic binuclear fragments {[Cu(hfac)<sub>2</sub>]<sub>2</sub>(NITmPhO3- Py)<sub>2</sub>} via the bridging unit [Cu(hfac)<sub>2</sub>];complex 2 presented a binuclear cyclic structure [Cu(hfac)<sub>2</sub>]<sub>2</sub>(NIToPhO3Py)<sub>2</sub>. The magnetic behaviors of the two complexes 1 and 2 have been investigated. Magnetic studies showed that antiferromagnetic interactions dominated in complex 1, while there existed ferromagnetic interactions between Cu(II) and coordinated NO group in complex 2.展开更多
Anodic oxidation of Co, Cu, Zn, and Sn metals in an acetone solution of 1,1-malonayl-bis(4-p- Chlorophenylthiosemicarbazide) yields complexes of composition with general formula [Co2(pClMaTS)(H2O)6]·2H2O, [Cu2(pC...Anodic oxidation of Co, Cu, Zn, and Sn metals in an acetone solution of 1,1-malonayl-bis(4-p- Chlorophenylthiosemicarbazide) yields complexes of composition with general formula [Co2(pClMaTS)(H2O)6]·2H2O, [Cu2(pClMaTS)(H2O)6], [Zn2(pClMaTS)(H2O)6] and [Sn2(pClMaTS)(H2O)6]·2H2O. Chelation was investigated based on elemental analysis, conductivity, magnetic moment, spectral (UV-Vis, IR, Raman, 1HNMR, mass), thermal, and ESR studies. The Raman and infrared spectral studies suggests the tridentate behavior of the ligand from each tail. Since the ligand has two thiose- micarbazide groups, it may acts in an SNO tridentate fashion from each side with one of the two metal ions forming a polynuclear complex coordinating through both of the lone pair of electrons the enolic oxygen of the carbonyl group (C=O), the azomethine nitrogen (C=N) and the thioenol form of the thiocarbonyl group (C=S). The differential thermogravimetric analysis (DTG) curves were used to study the decomposition steps of the isolated complexes using Horowitz-Metzger (HM) and Coats-Redfern (CR) methods. The kinetic thermodynamic parameters such as: E*, ΔH*, ΔS*and ΔG* are calculated from the DTG curves.展开更多
The platinum (II) complexes of the [Pt (N4,N7-Ribavirin) (DMSO) Cl], [Pt (N4,N7-De-oxyribavirin) (DMSO) Cl] were obtained by the reactions of cis-[Pt (DMSO)2 Cl2] and K[Pt (DMSO) Cl3] with 1-??-D-ribofuranosyl-1,2,4-t...The platinum (II) complexes of the [Pt (N4,N7-Ribavirin) (DMSO) Cl], [Pt (N4,N7-De-oxyribavirin) (DMSO) Cl] were obtained by the reactions of cis-[Pt (DMSO)2 Cl2] and K[Pt (DMSO) Cl3] with 1-??-D-ribofuranosyl-1,2,4-triazole-3-carboxamide (Ribavirin) and its deoxy-analogue (deoxyribavirin). The preparation of 1-(2'-deoxy-?-D-ribofuranosyl) -1,2,4-triazole-3-carboxamide was also performed through a four-step procedure, protection of 3', 5'-dihydroxyl group of Ribavirin with 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane (TPDS-Cl), phenoxythio-carbonylation of the 2'-hydroxyl group of 3', 5'-O-TPDS-Ribavirin with phenoxythiocarbonyl-chloride (PTC-Cl), reduction of 2′-O-phenoxythiocarbonyl ester of 3', 5'-O-TPDS-Ribavirin with tri-n-butyltin hydride and AIBN, deprotection of 3', 5'-O-TPDS-Ribavirin with tetrabutylammon-ium fluoride in THF.展开更多
Oxygenation constants and thermodynamic parameters DeltaH degrees and DeltaS degrees of cobalt (II) complexes with bis-(furaldehyde) Schiff bases (1, 2, 3, 4)were obtained by mearsuring saturated dioxygen uptake of th...Oxygenation constants and thermodynamic parameters DeltaH degrees and DeltaS degrees of cobalt (II) complexes with bis-(furaldehyde) Schiff bases (1, 2, 3, 4)were obtained by mearsuring saturated dioxygen uptake of these complexes in pyridine at different temperature. These complexes could activate molecular oxygen and were used as catalysts in cyclohexene oxidation. The influence of ligand structure on the dioxygen affinity and catalytic activity of the complexes were discussed.展开更多
The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was det...The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was determined by single-crystal X-ray diffraction method. It crys- tallizes in triclinic, space group P1, C44H31ClCu2N4O12, Mr = 970.26, a = 8.175(2), b = 16.254(4), c = 16.946(4) ?, α = 62.966(6), β = 84.833(8), γ = 84.348(8)°, V = 1993.4(8) ?3, Z = 2, Dc = 1.616 g/cm3, F(000) = 988 and μ = 1.207 mm-1. The final R = 0.0429 and wR = 0.0843 for 5682 observed reflections with I > 2σ(I). Each copper(II) atom displays a distorted square-pyramidal geometry with two nitrogen atoms of one chelate 2,2?-bipy molecule, two oxygen atoms from two different bridging carboxylate groups of Hpht- and one bridging chloride atom occupying the apical position. The two copper(II) atoms are connected by a μ2-Cl atom and two bridging Hpht- ligands in a syn-syn coordination mode to form an isolated dinuclear unit. The molecular structure is extended to a one-dimensional wavy chain through hydrogen bonds. The title complex exhibits blue fluorescent emission at 443 nm (λex = 372 nm) in the solid state at room temperature.展开更多
A new zinc(II) complex, Zn(2-NH2py)2Br2 (py=pyridine), has been synthesized, and its molecular structure has been confirmed by IR, elemental analysis and -ray crystal structure analysis. Its space group is P21/n with...A new zinc(II) complex, Zn(2-NH2py)2Br2 (py=pyridine), has been synthesized, and its molecular structure has been confirmed by IR, elemental analysis and -ray crystal structure analysis. Its space group is P21/n with Mr=413.43 (C10H12Br2N4Zn), a=7.435(2), b=12.865(3), c=14.186(4)? b=94.08(2)? V=1353.5(5) 3, Z=4, Dc=2.029 g/cm3, F(000)=328, ?2.378mm-1, R=0.0283, wR=0.0501. The total observed reflections with I≥2?I) were 5314, of which the independent reflections were 3106. The complex structure contains a distorted tetrahedron formed by four atoms coordinated to zinc atom, namely two bromide atoms and two nitrogen atoms. The two ZnBr bond lengths within one molecule, 2.3763(6) and 2.4002(5)? respectively, are not equal; and so are the two ZnN bond lengths, which are 2.031(2) and 2.044(2)?respectively. The calculation results using PM3 method through MOPAC software package in Chem 3D show that its first molecular hyperpolarizability b value is 5.210-30esu, which is comparable with that of p-nitroaniline. No bulk SHG effect has been detected due to the centrosymmetric space group.展开更多
The adsorption behaviour of Cu2+ onto maghnite was conducted under batch conditions. The effect of time, pH of the dispersion, temperature and initial metal concentration on the adsorption of Cu2+ onto maghnite was in...The adsorption behaviour of Cu2+ onto maghnite was conducted under batch conditions. The effect of time, pH of the dispersion, temperature and initial metal concentration on the adsorption of Cu2+ onto maghnite was investigated. In this study, 94% of Cu(II), was adsorbed on the maghnite clay when the equilibrium was reached at 120 min. The adsorption of Cu2+ was a fast process that followed the pseudo-second-order kinetics. This process could be described by the Langmuir model and gave a maximum Cu2+ adsorption capacity of 21.78 mg/g at 293 K. The thermodynamic parameters such as variation of enthalpy ΔH, variation of entropy ΔS and variation of Gibbs free energy ΔG were calculated from the slope and intercept of lnKd vs. 1/T plots. The adsorption was endothermic reaction. The adsorption process for this natural maghnite is more spontaneous because the values of ΔG are less negative. The results suggested that natural maghnite was suitable as sorbent material for the recovery and adsorption of metal ion from aqueous solutions.展开更多
A new dinuclear copper(II) complex ([Cu(C12H17N2O)(N3)]2, C24H34Cu2N10O2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the monoclinic system, space group P21/c with a =...A new dinuclear copper(II) complex ([Cu(C12H17N2O)(N3)]2, C24H34Cu2N10O2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the monoclinic system, space group P21/c with a = 18.529(4), b = 10.933(2), c = 14.534(3) ?, β = 111.07(3)°, V = 2748(1) ?3, Z = 4, Mr = 621.69, F(000) = 1288, Dc = 1.503 g/cm3 and μ(MoKα) = 1.590 mm?1. The structure was refined to R = 0.0647 and wR = 0.1846 for 4406 observed reflections (I > 2σ(I)). The asymmetric unit comprises two halfmolecules. The complex is a centrosymmetric dimmer in which the copper atoms are penta-coordinated by three coordination atoms from the corresponding tridentate Schiff base ligand and two bridging azide anions. The Cu(II)…Cu(II) average distance is 3.350(1) ?.展开更多
A new copper(II)-2,2'-biimidazole metal-organic POMs-supported compound [Cu(H2biim)2]{[Cu(H2biim)212[H10W12O44]}'8H2O (H2biim = 2,2'-biimidazole) has been success- fully synthesized under hydrothermal condi...A new copper(II)-2,2'-biimidazole metal-organic POMs-supported compound [Cu(H2biim)2]{[Cu(H2biim)212[H10W12O44]}'8H2O (H2biim = 2,2'-biimidazole) has been success- fully synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and TG. The crystal adopts space group Pi with a = 11.800(2), b = 13.437(3), c = 13.685(3) A, V = 1922.5(7) A3, D,. = 3.507 g/cm3, C36H62Cu3N24W12O52, M,. = 4059.92, F(000) = 1837,μ = 18.796 mm-1, Z = 1, R = 0.0579 and wR = 0.1465 for 8734 observed reflections (I 〉 2σ(I)). X-ray crystallography analysis exhibits that the title compound consists of one [H10W12044]6- polyanion and three [Cu(H2biim)2] units. And significant π-π stacking interactions and intermolecular O-H-,.O or N-H.'-O hydrogen-bonding interactions lead to a three-dimensional supramolecular framework. Thermal stability and magnetic property of the complex have also been investigated.展开更多
Schiff base derived from 2-aminophenol and 3-formyl-2-hydroxy-6-methoxyquinoline and its Mn(II) and Fe(II) complexes were synthesized and characterized by melting point and decomposition temperature, elemental analysi...Schiff base derived from 2-aminophenol and 3-formyl-2-hydroxy-6-methoxyquinoline and its Mn(II) and Fe(II) complexes were synthesized and characterized by melting point and decomposition temperature, elemental analysis, molar conductivity, infrared (IR) spectral analysis, atomic absorption spectroscopy (AAS) analysis, solubility test, and magnetic susceptibility. The Fourier-transform infrared spectroscopy (FTIR) spectral data of the Schiff base determined showed <span><span style="font-family:Verdana;">a band at 1622 cm</span><sup><span style="font-family:Verdana;"><span style="white-space:nowrap;"><span style="white-space:nowrap;"><span style="white-space:nowrap;">−</span></span></span>1</span></sup><span style="font-family:Verdana;"> and this was assigned to the </span><i><span style="font-family:Verdana;">v </span></i><span style="font-family:Verdana;">(C=N), which is a feature of azomethine group. The same band was observed to shift to lower frequencies 1577 and 1599 cm</span><sup><span style="font-family:Verdana;"><span style="white-space:nowrap;"><span style="white-space:nowrap;"><span style="white-space:nowrap;">−</span></span></span>1</span></sup><span style="font-family:Verdana;"> in the complexes suggesting coordination of the Schiff base with the respective metal(II) ions. Molar conductan</span></span><span><span style="font-family:Verdana;">ce values 14.58 and 12.65 Ω</span><sup><span style="font-family:Verdana;"><span style="white-space:nowrap;"><span style="white-space:nowrap;"><span style="white-space:nowrap;">−</span></span></span>1</span></sup><span style="font-family:Verdana;"><span style="white-space:nowrap;"><span style="white-space:nowrap;"><span style="white-space:nowrap;">∙</span></span></span>cm</span><sup><span style="font-family:Verdana;">2</span></sup><span style="font-family:Verdana;"><span style="white-space:nowrap;"><span style="white-space:nowrap;"><span style="white-space:nowrap;">∙</span></span></span>mol</span><sup><span style="font-family:Verdana;"><span style="white-space:nowrap;"><span style="white-space:nowrap;"><span style="white-space:nowrap;">−</span></span></span>1</span></sup><span style="font-family:Verdana;"> show that the metal complexes were non-electrolyte in nature. The magnetic susceptibility of the complexes was determined and the gram magnetic susceptibility of the complexes was found to be positive, revealing that they are paramagnetic. The elemental analysis of the complexes for C, N and H determined suggested 1:1 metal to ligand ratio. The result of the antimicrobial studies showed that, the metal(II) complexes exhibited better antibacterial and antifungal activity than the Schiff base.</span></span>展开更多
Adsorption of Cu(II) and Co(II) from aqueous solutions on synthetic nano Fe3O4 has been studied. The effect of experimental parameters such as initial concentration of the metal ions, adsorbent dosage, contact time an...Adsorption of Cu(II) and Co(II) from aqueous solutions on synthetic nano Fe3O4 has been studied. The effect of experimental parameters such as initial concentration of the metal ions, adsorbent dosage, contact time and pH has been investigated. Optimum removal efficiency of Cu(II) ion was found to be 97.8% with the dose rate of 1.07 g/L in 60 minutes at pH = 5.5 and for Co(II) ion, it was found to be 99.2% with the dose rate of2.57 g/L in 10 minutes at pH = 5.4. The removal of Co(II) ions require only 10 minutes with the efficient removal of 99.2%, whereas Cu(II) ions require 60 minutes with the maximum removal of 97.8%. In order to understand the effective removal of Cu(II) and Co(II) ions on Fe3O4, room temperature magnetic measurement was carried out using Vibrational Spectrum Magnetometer (VSM), before and after adsorption with a maximum applied magnetic field of 20,000 G.展开更多
A new dinuclear copper(II) complex (Cu(C12H17N2O)(NCS)2, C26H34Cu2N6O2S2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclinic system, space group P1 with a = 11....A new dinuclear copper(II) complex (Cu(C12H17N2O)(NCS)2, C26H34Cu2N6O2S2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclinic system, space group P1 with a = 11.289(2), b = 12.071(2), c = 12.113(2) ?, α = 72.90(3), β = 83.76(3), γ = 65.60(3)°, V = 1436.7(5) ?3, Z = 2, Mr = 653.79, F(000) = 676, Dc = 1.511 g/cm3, μ(MoKα) = 1.660 mm?1, the final R = 0.0334 and wR = 0.0856 for 5047 observed reflections (I > 2σ(I)). The asymmetric unit comprises two half-molecules. The complex is a centrosymmetric dimmer in which each copper(II) is coordinated in the equatorial plane to the N-(salicylidene)-3- dimethylaminopropylamine ligand through the deprotonated phenolic oxygen atom as well as the nitrogen atoms of imine and amine. The fourth coordination site is occupied by the nitrogen atom of NCS?, while the axial one by the symmetrically related phenoxy oxygen of the other monomeric unit. The Cu(II)…Cu(II) average distance is 3.110(1) ?.展开更多
At room temperature,dibenzoyl peroxide undergoes oxidative addition on metallic Copper Powder and 2-aminopyridine in a solvent(acetone and tetrahydrofuran), which affords the product as a binuclear Cu(II)complex [Cu (...At room temperature,dibenzoyl peroxide undergoes oxidative addition on metallic Copper Powder and 2-aminopyridine in a solvent(acetone and tetrahydrofuran), which affords the product as a binuclear Cu(II)complex [Cu (C5 H5 COO)2(C5 H5 N2)]2. (C4 H5 O)2. The structure of the complex was characterized by elemental analyses. IR spectra, TG-DTA. The structure of the compound has been solved by direct method and Fourier synthesis, and refined by block-diagonal and full matrix least-squares method to a final R of 0.04329 for 3671 independent reflection of I>e(I). The crystals are triclinic, C46H45N4O10Cu2.Z=1, Mr=943.93, space group P-1, with cell parameters, a=10.806(1); b=11.169(3);c=11.729(2)A; α=71.99(2),β=89.38(1)°; γ=81.37(1); V=1330.1A3; Dc=1.172g.cm-3;μ=8.5cm-1. The copper(II) ion is coordinated by four bridging bidentate benzoate and two 2-aminopyridine to form dimeric molecules.展开更多
Two homochiral metallosalen complexes, Ni(salen) (salen = (1R,2R)-(-)-diamino- cyclohexane-N,N′-bis(3-tert-butyl-5-(4′-benzoic acid)-salicylidene) 1 and Cu(salen) 2, have been synthesized and characteri...Two homochiral metallosalen complexes, Ni(salen) (salen = (1R,2R)-(-)-diamino- cyclohexane-N,N′-bis(3-tert-butyl-5-(4′-benzoic acid)-salicylidene) 1 and Cu(salen) 2, have been synthesized and characterized by IR, microanalysis, TGA, powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P21212 with Z = 4. For 1, a = 12.082(2), b = 15.447(3), c = 18.784(4)A^°, V= 3505.7(12)A^°3, Mr = 731.50, Dc = 1.386 g/cm^3, μ = 0.606 mm^-1, F(000) = 1544, the final GOOF = 1.043, R = 0.0496 and wR = 0.1248 for 4791 observed reflections with I 〉 2σ(I). For 2, a = 12.181(2), b = 15.501(3), c = 18.877(4) A^°, V = 3564.3(12)A^°3, Mr = 736.33, Dc = 1.372 g/cm^3, μ = 0.665 mm^-1, F(000) = 1548, the final GOOF = 1.062, R = 0.0575 and wR = 0.1508 for 4562 observed reflections with I 〉 2σ(I). The crystal structures of 1 and 2 are isostructural with very similar supramolecular structures. An infinite two-dimensional network is generated by hydrogen bonding interactions and intermolecular π…π interactions.展开更多
The uptake kinetics of platinum(II)complexes of 1,2 -diaminocyclohexane(dach)isomers(1R,2R-dach, 1R,2S-dach. 1S,2S-dach) with various leaving groups, Chloride(CI), oxalate (OX),squaric acid(SA), and demethylcantharic ...The uptake kinetics of platinum(II)complexes of 1,2 -diaminocyclohexane(dach)isomers(1R,2R-dach, 1R,2S-dach. 1S,2S-dach) with various leaving groups, Chloride(CI), oxalate (OX),squaric acid(SA), and demethylcantharic acid (DA) was studied in the plasma isotonic buffer. The experimentalresults show that across-membrane transport of all the platinum complexes studied follows a firstorder Kinetic process and a passive diffustion mechanism. The uptake rate constants of these platinum(II)complexes decrease in the following sequence with the k value(h-1):CI>SA>OX>DA. It isnoteworthy that the k values of the platinum(II)complexes with same leaving group reduce as: 1R,2R-dach>1R,2S-dach>1S,2S-dach. Based on these results, it is firstly suggested that the erythocytemembrane recognizes the chirality of these platinum complexes.展开更多
基金supported by NNSFC (20971085)"973" Programs (2007CB209701 and 2009CB930403)the Key Project and Scientific Research Foundation for the Returned Overseas Chinese Scholars of State Education Ministry
文摘Two homochiral mercury (1) and cadmium (2) complexes derived from chiral twisted biphenyl pyridine ligand (3,3'-bipyridine-5,5',6,6'-tetramethyl-2,2'-dimethoxy-1,1'-biphenyl) have been synthesized and characterized by IR, microanalysis, TGA, UV-Vis, powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P21212 with Z = 2. For 1, a = 14.2038(16), b = 14.3630(17), c = 7.0257(8), V = 1433.3(3)3, Mr = 878.91, Dc = 2.037 g/cm3, μ = 7.549 mm-1, F(000) = 824, the final GOF = 1.017, R = 0.0296 and wR = 0.0645 for 2925 observed reflections with I 2σ(I). For 2, a = 14.212(3), b = 14.392(3), c = 7.0498(14), V = 1442.0(5)3, Mr = 790.72, Dc = 1.821 g/cm3, μ = 2.924 mm–1, F(000) = 760, the final GOF = 1.075, R = 0.0340 and wR = 0.0834 for 3144 observed reflections with I 2σ(I). The crystal structures of 1 and 2 are isostructural and each adopts a two-dimensional supramolecular network which contains the C–H···π interactions.
文摘Novel polymeric Cu<sup>2+</sup> complexes derived from the reaction of cyanoacetylhydrazine (<strong>CAH</strong>;<strong>L</strong>) with CuCl<sub>2</sub>•2H<sub>2</sub>O in different solvents were synthesized and characterized. The isolated solid polymeric complexes were investigated using modern conventional physicochemical and spectral (IR, <sup>1</sup>H-NMR, UV-Vis. ESR, Raman), magnetic and thermal studies. The results revealed that <strong>CAH</strong> behaves in different ways towards the coordination of the Cu<sup>2+</sup> ion. The promotion of solvents to the cyano group was discussed on the basis of the solvent and the Cu<sup>2+</sup> ion used. Magnetic and spectral studies suggest octahedral geometry is proposed for the Cu<sup>2+</sup> complexes. EPR studies indicate the existence of polymeric complexes depending on the results of <i>g</i>-values. The results suggest that the number of copper atoms ranges from three to twelve atoms. The molecular modeling is drawn and some chemical characteristics are calculated such as chemical reactivity and energy components are investigated between the different types of the ligands.
文摘The ternary complexes containing Cu(II),L-His and nucleotide (5'-GMP and 5'-IMP)were synthesized and characterized.IR and ~1H NMR spectra show that Cu(II)binds to carboxylate oxygen and imidazole nitrogen of L-His and purine N_7 of 5'-GMP and 5'-IMP.The interaction of Cu(II)with Po_3^(2-)of 5'-GMP is present,but that for 5'-IMP is not present.
文摘The synthesis and structural characterization of cobalt(II) complexes of amino acid Schiff bases was prepared from Salicylaldehyde and three amino acid (Valine, Leucine, and Isoleucine)?in basic medium. The metal complexes was synthesized by treating an ethanolic solution of the ligand with appropriate amount of metal salts [1:2] [M:L] ratio. The synthesized Schiff bases and their metal complexes have been investigated on the bases of elemental chemical analysis, FTIR, electronic spectral,?1HNMR,?13CNMR, MS, molar conductance and magnetic susceptibility measurements. The electronic spectra of the metal complexes and their magnetic susceptibility measurements suggest octahedral structures are the probable coordination geometries for the isolated complexes. The Schiff bases and their metal complexes were preliminary scanned against various strains of microbes to study their biological effect.
文摘Using two new flexible and functional nitronyl nitroxide radicals as ligands, two copper (II) complexes {[Cu(hfac)<sub>2</sub>]<sub>3</sub>(NITmPhO3Py)<sub>2</sub>}<sub>n</sub> (1) and [Cu(hfac)<sub>2</sub><sub> </sub>(NIToPhO3Py)]<sub>2</sub> (2) (NITmPhO3Py = 2-[(3-methoxy-pyridinyl)phen-3-yl]- 4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, NIToPhO3Py = 2-[(3-methoxy-pyridinyl)phen-2-ly]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, hfac = hexafluoroacetylacetone), have been characterized structurally and magnetically. The X-ray crystal analyses showed that complex 1 displayed a chain polymer structure which formed with {[Cu(hfac)<sub>2</sub>]<sub>3</sub>(NITmPhO3Py)<sub>2</sub>}<sub>n</sub> due to the cross-linking of two cyclic binuclear fragments {[Cu(hfac)<sub>2</sub>]<sub>2</sub>(NITmPhO3- Py)<sub>2</sub>} via the bridging unit [Cu(hfac)<sub>2</sub>];complex 2 presented a binuclear cyclic structure [Cu(hfac)<sub>2</sub>]<sub>2</sub>(NIToPhO3Py)<sub>2</sub>. The magnetic behaviors of the two complexes 1 and 2 have been investigated. Magnetic studies showed that antiferromagnetic interactions dominated in complex 1, while there existed ferromagnetic interactions between Cu(II) and coordinated NO group in complex 2.
文摘Anodic oxidation of Co, Cu, Zn, and Sn metals in an acetone solution of 1,1-malonayl-bis(4-p- Chlorophenylthiosemicarbazide) yields complexes of composition with general formula [Co2(pClMaTS)(H2O)6]·2H2O, [Cu2(pClMaTS)(H2O)6], [Zn2(pClMaTS)(H2O)6] and [Sn2(pClMaTS)(H2O)6]·2H2O. Chelation was investigated based on elemental analysis, conductivity, magnetic moment, spectral (UV-Vis, IR, Raman, 1HNMR, mass), thermal, and ESR studies. The Raman and infrared spectral studies suggests the tridentate behavior of the ligand from each tail. Since the ligand has two thiose- micarbazide groups, it may acts in an SNO tridentate fashion from each side with one of the two metal ions forming a polynuclear complex coordinating through both of the lone pair of electrons the enolic oxygen of the carbonyl group (C=O), the azomethine nitrogen (C=N) and the thioenol form of the thiocarbonyl group (C=S). The differential thermogravimetric analysis (DTG) curves were used to study the decomposition steps of the isolated complexes using Horowitz-Metzger (HM) and Coats-Redfern (CR) methods. The kinetic thermodynamic parameters such as: E*, ΔH*, ΔS*and ΔG* are calculated from the DTG curves.
文摘The platinum (II) complexes of the [Pt (N4,N7-Ribavirin) (DMSO) Cl], [Pt (N4,N7-De-oxyribavirin) (DMSO) Cl] were obtained by the reactions of cis-[Pt (DMSO)2 Cl2] and K[Pt (DMSO) Cl3] with 1-??-D-ribofuranosyl-1,2,4-triazole-3-carboxamide (Ribavirin) and its deoxy-analogue (deoxyribavirin). The preparation of 1-(2'-deoxy-?-D-ribofuranosyl) -1,2,4-triazole-3-carboxamide was also performed through a four-step procedure, protection of 3', 5'-dihydroxyl group of Ribavirin with 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane (TPDS-Cl), phenoxythio-carbonylation of the 2'-hydroxyl group of 3', 5'-O-TPDS-Ribavirin with phenoxythiocarbonyl-chloride (PTC-Cl), reduction of 2′-O-phenoxythiocarbonyl ester of 3', 5'-O-TPDS-Ribavirin with tri-n-butyltin hydride and AIBN, deprotection of 3', 5'-O-TPDS-Ribavirin with tetrabutylammon-ium fluoride in THF.
文摘Oxygenation constants and thermodynamic parameters DeltaH degrees and DeltaS degrees of cobalt (II) complexes with bis-(furaldehyde) Schiff bases (1, 2, 3, 4)were obtained by mearsuring saturated dioxygen uptake of these complexes in pyridine at different temperature. These complexes could activate molecular oxygen and were used as catalysts in cyclohexene oxidation. The influence of ligand structure on the dioxygen affinity and catalytic activity of the complexes were discussed.
基金This work was supported by the National Natural Science Foundation of China (20001007 20131020)+1 种基金and Natural Science Foundation of Fujian Province (2003I031 A0420002)
文摘The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was determined by single-crystal X-ray diffraction method. It crys- tallizes in triclinic, space group P1, C44H31ClCu2N4O12, Mr = 970.26, a = 8.175(2), b = 16.254(4), c = 16.946(4) ?, α = 62.966(6), β = 84.833(8), γ = 84.348(8)°, V = 1993.4(8) ?3, Z = 2, Dc = 1.616 g/cm3, F(000) = 988 and μ = 1.207 mm-1. The final R = 0.0429 and wR = 0.0843 for 5682 observed reflections with I > 2σ(I). Each copper(II) atom displays a distorted square-pyramidal geometry with two nitrogen atoms of one chelate 2,2?-bipy molecule, two oxygen atoms from two different bridging carboxylate groups of Hpht- and one bridging chloride atom occupying the apical position. The two copper(II) atoms are connected by a μ2-Cl atom and two bridging Hpht- ligands in a syn-syn coordination mode to form an isolated dinuclear unit. The molecular structure is extended to a one-dimensional wavy chain through hydrogen bonds. The title complex exhibits blue fluorescent emission at 443 nm (λex = 372 nm) in the solid state at room temperature.
基金This work was financed by the National Key Fundamental Research Program of China.
文摘A new zinc(II) complex, Zn(2-NH2py)2Br2 (py=pyridine), has been synthesized, and its molecular structure has been confirmed by IR, elemental analysis and -ray crystal structure analysis. Its space group is P21/n with Mr=413.43 (C10H12Br2N4Zn), a=7.435(2), b=12.865(3), c=14.186(4)? b=94.08(2)? V=1353.5(5) 3, Z=4, Dc=2.029 g/cm3, F(000)=328, ?2.378mm-1, R=0.0283, wR=0.0501. The total observed reflections with I≥2?I) were 5314, of which the independent reflections were 3106. The complex structure contains a distorted tetrahedron formed by four atoms coordinated to zinc atom, namely two bromide atoms and two nitrogen atoms. The two ZnBr bond lengths within one molecule, 2.3763(6) and 2.4002(5)? respectively, are not equal; and so are the two ZnN bond lengths, which are 2.031(2) and 2.044(2)?respectively. The calculation results using PM3 method through MOPAC software package in Chem 3D show that its first molecular hyperpolarizability b value is 5.210-30esu, which is comparable with that of p-nitroaniline. No bulk SHG effect has been detected due to the centrosymmetric space group.
文摘The adsorption behaviour of Cu2+ onto maghnite was conducted under batch conditions. The effect of time, pH of the dispersion, temperature and initial metal concentration on the adsorption of Cu2+ onto maghnite was investigated. In this study, 94% of Cu(II), was adsorbed on the maghnite clay when the equilibrium was reached at 120 min. The adsorption of Cu2+ was a fast process that followed the pseudo-second-order kinetics. This process could be described by the Langmuir model and gave a maximum Cu2+ adsorption capacity of 21.78 mg/g at 293 K. The thermodynamic parameters such as variation of enthalpy ΔH, variation of entropy ΔS and variation of Gibbs free energy ΔG were calculated from the slope and intercept of lnKd vs. 1/T plots. The adsorption was endothermic reaction. The adsorption process for this natural maghnite is more spontaneous because the values of ΔG are less negative. The results suggested that natural maghnite was suitable as sorbent material for the recovery and adsorption of metal ion from aqueous solutions.
文摘A new dinuclear copper(II) complex ([Cu(C12H17N2O)(N3)]2, C24H34Cu2N10O2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the monoclinic system, space group P21/c with a = 18.529(4), b = 10.933(2), c = 14.534(3) ?, β = 111.07(3)°, V = 2748(1) ?3, Z = 4, Mr = 621.69, F(000) = 1288, Dc = 1.503 g/cm3 and μ(MoKα) = 1.590 mm?1. The structure was refined to R = 0.0647 and wR = 0.1846 for 4406 observed reflections (I > 2σ(I)). The asymmetric unit comprises two halfmolecules. The complex is a centrosymmetric dimmer in which the copper atoms are penta-coordinated by three coordination atoms from the corresponding tridentate Schiff base ligand and two bridging azide anions. The Cu(II)…Cu(II) average distance is 3.350(1) ?.
基金supported by the Knowledge Innovation Program(No.KJCX2-EW-H01)of Chinese Academy of SciencesNational Natural Science Foundation of China(No.21003125,21073190)Natural Science Foundation of Fujian Province(2010J05040,2010J01057)
文摘A new copper(II)-2,2'-biimidazole metal-organic POMs-supported compound [Cu(H2biim)2]{[Cu(H2biim)212[H10W12O44]}'8H2O (H2biim = 2,2'-biimidazole) has been success- fully synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and TG. The crystal adopts space group Pi with a = 11.800(2), b = 13.437(3), c = 13.685(3) A, V = 1922.5(7) A3, D,. = 3.507 g/cm3, C36H62Cu3N24W12O52, M,. = 4059.92, F(000) = 1837,μ = 18.796 mm-1, Z = 1, R = 0.0579 and wR = 0.1465 for 8734 observed reflections (I 〉 2σ(I)). X-ray crystallography analysis exhibits that the title compound consists of one [H10W12044]6- polyanion and three [Cu(H2biim)2] units. And significant π-π stacking interactions and intermolecular O-H-,.O or N-H.'-O hydrogen-bonding interactions lead to a three-dimensional supramolecular framework. Thermal stability and magnetic property of the complex have also been investigated.
文摘Schiff base derived from 2-aminophenol and 3-formyl-2-hydroxy-6-methoxyquinoline and its Mn(II) and Fe(II) complexes were synthesized and characterized by melting point and decomposition temperature, elemental analysis, molar conductivity, infrared (IR) spectral analysis, atomic absorption spectroscopy (AAS) analysis, solubility test, and magnetic susceptibility. The Fourier-transform infrared spectroscopy (FTIR) spectral data of the Schiff base determined showed <span><span style="font-family:Verdana;">a band at 1622 cm</span><sup><span style="font-family:Verdana;"><span style="white-space:nowrap;"><span style="white-space:nowrap;"><span style="white-space:nowrap;">−</span></span></span>1</span></sup><span style="font-family:Verdana;"> and this was assigned to the </span><i><span style="font-family:Verdana;">v </span></i><span style="font-family:Verdana;">(C=N), which is a feature of azomethine group. The same band was observed to shift to lower frequencies 1577 and 1599 cm</span><sup><span style="font-family:Verdana;"><span style="white-space:nowrap;"><span style="white-space:nowrap;"><span style="white-space:nowrap;">−</span></span></span>1</span></sup><span style="font-family:Verdana;"> in the complexes suggesting coordination of the Schiff base with the respective metal(II) ions. Molar conductan</span></span><span><span style="font-family:Verdana;">ce values 14.58 and 12.65 Ω</span><sup><span style="font-family:Verdana;"><span style="white-space:nowrap;"><span style="white-space:nowrap;"><span style="white-space:nowrap;">−</span></span></span>1</span></sup><span style="font-family:Verdana;"><span style="white-space:nowrap;"><span style="white-space:nowrap;"><span style="white-space:nowrap;">∙</span></span></span>cm</span><sup><span style="font-family:Verdana;">2</span></sup><span style="font-family:Verdana;"><span style="white-space:nowrap;"><span style="white-space:nowrap;"><span style="white-space:nowrap;">∙</span></span></span>mol</span><sup><span style="font-family:Verdana;"><span style="white-space:nowrap;"><span style="white-space:nowrap;"><span style="white-space:nowrap;">−</span></span></span>1</span></sup><span style="font-family:Verdana;"> show that the metal complexes were non-electrolyte in nature. The magnetic susceptibility of the complexes was determined and the gram magnetic susceptibility of the complexes was found to be positive, revealing that they are paramagnetic. The elemental analysis of the complexes for C, N and H determined suggested 1:1 metal to ligand ratio. The result of the antimicrobial studies showed that, the metal(II) complexes exhibited better antibacterial and antifungal activity than the Schiff base.</span></span>
文摘Adsorption of Cu(II) and Co(II) from aqueous solutions on synthetic nano Fe3O4 has been studied. The effect of experimental parameters such as initial concentration of the metal ions, adsorbent dosage, contact time and pH has been investigated. Optimum removal efficiency of Cu(II) ion was found to be 97.8% with the dose rate of 1.07 g/L in 60 minutes at pH = 5.5 and for Co(II) ion, it was found to be 99.2% with the dose rate of2.57 g/L in 10 minutes at pH = 5.4. The removal of Co(II) ions require only 10 minutes with the efficient removal of 99.2%, whereas Cu(II) ions require 60 minutes with the maximum removal of 97.8%. In order to understand the effective removal of Cu(II) and Co(II) ions on Fe3O4, room temperature magnetic measurement was carried out using Vibrational Spectrum Magnetometer (VSM), before and after adsorption with a maximum applied magnetic field of 20,000 G.
文摘A new dinuclear copper(II) complex (Cu(C12H17N2O)(NCS)2, C26H34Cu2N6O2S2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclinic system, space group P1 with a = 11.289(2), b = 12.071(2), c = 12.113(2) ?, α = 72.90(3), β = 83.76(3), γ = 65.60(3)°, V = 1436.7(5) ?3, Z = 2, Mr = 653.79, F(000) = 676, Dc = 1.511 g/cm3, μ(MoKα) = 1.660 mm?1, the final R = 0.0334 and wR = 0.0856 for 5047 observed reflections (I > 2σ(I)). The asymmetric unit comprises two half-molecules. The complex is a centrosymmetric dimmer in which each copper(II) is coordinated in the equatorial plane to the N-(salicylidene)-3- dimethylaminopropylamine ligand through the deprotonated phenolic oxygen atom as well as the nitrogen atoms of imine and amine. The fourth coordination site is occupied by the nitrogen atom of NCS?, while the axial one by the symmetrically related phenoxy oxygen of the other monomeric unit. The Cu(II)…Cu(II) average distance is 3.110(1) ?.
文摘At room temperature,dibenzoyl peroxide undergoes oxidative addition on metallic Copper Powder and 2-aminopyridine in a solvent(acetone and tetrahydrofuran), which affords the product as a binuclear Cu(II)complex [Cu (C5 H5 COO)2(C5 H5 N2)]2. (C4 H5 O)2. The structure of the complex was characterized by elemental analyses. IR spectra, TG-DTA. The structure of the compound has been solved by direct method and Fourier synthesis, and refined by block-diagonal and full matrix least-squares method to a final R of 0.04329 for 3671 independent reflection of I>e(I). The crystals are triclinic, C46H45N4O10Cu2.Z=1, Mr=943.93, space group P-1, with cell parameters, a=10.806(1); b=11.169(3);c=11.729(2)A; α=71.99(2),β=89.38(1)°; γ=81.37(1); V=1330.1A3; Dc=1.172g.cm-3;μ=8.5cm-1. The copper(II) ion is coordinated by four bridging bidentate benzoate and two 2-aminopyridine to form dimeric molecules.
基金supported by the Natural Science Foundation of Anhui Province (No. KJ2008B166)
文摘Two homochiral metallosalen complexes, Ni(salen) (salen = (1R,2R)-(-)-diamino- cyclohexane-N,N′-bis(3-tert-butyl-5-(4′-benzoic acid)-salicylidene) 1 and Cu(salen) 2, have been synthesized and characterized by IR, microanalysis, TGA, powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P21212 with Z = 4. For 1, a = 12.082(2), b = 15.447(3), c = 18.784(4)A^°, V= 3505.7(12)A^°3, Mr = 731.50, Dc = 1.386 g/cm^3, μ = 0.606 mm^-1, F(000) = 1544, the final GOOF = 1.043, R = 0.0496 and wR = 0.1248 for 4791 observed reflections with I 〉 2σ(I). For 2, a = 12.181(2), b = 15.501(3), c = 18.877(4) A^°, V = 3564.3(12)A^°3, Mr = 736.33, Dc = 1.372 g/cm^3, μ = 0.665 mm^-1, F(000) = 1548, the final GOOF = 1.062, R = 0.0575 and wR = 0.1508 for 4562 observed reflections with I 〉 2σ(I). The crystal structures of 1 and 2 are isostructural with very similar supramolecular structures. An infinite two-dimensional network is generated by hydrogen bonding interactions and intermolecular π…π interactions.
文摘The uptake kinetics of platinum(II)complexes of 1,2 -diaminocyclohexane(dach)isomers(1R,2R-dach, 1R,2S-dach. 1S,2S-dach) with various leaving groups, Chloride(CI), oxalate (OX),squaric acid(SA), and demethylcantharic acid (DA) was studied in the plasma isotonic buffer. The experimentalresults show that across-membrane transport of all the platinum complexes studied follows a firstorder Kinetic process and a passive diffustion mechanism. The uptake rate constants of these platinum(II)complexes decrease in the following sequence with the k value(h-1):CI>SA>OX>DA. It isnoteworthy that the k values of the platinum(II)complexes with same leaving group reduce as: 1R,2R-dach>1R,2S-dach>1S,2S-dach. Based on these results, it is firstly suggested that the erythocytemembrane recognizes the chirality of these platinum complexes.