Aggregation properties of bis(salicylaldiminato)zinc(II) Schiff-base complexes and their Lewis acidic character

The synthesis, characterization, (1)H NMR, optical absorption and fluorescent properties of a series of amphiphilic Schiff-base bis(salicylaldiminato)zinc(II) complexes are reported. Detailed (1)H NMR, DOSY NMR, optical absorption and fluorescence spectroscopy studies indicate the existence of aggregate species in solutions of non-coordinating solvents. The degree of aggregation is related to the nature of the bridging diamine. Chloroform solutions of complexes where the bridging diamine contains a naphthalene or the pyridine nucleus are always characterized by the presence of defined dimer aggregates, whereas oligomeric aggregates are likely formed by complexes where the bridging diamine contains a benzene ring. In coordinating solvents or in the presence of coordinating species, a complete deaggregation of the complexes occurs, because of the axial coordination to the Zn(II) ion, accompanied by considerable changes in the (1)H NMR and optical absorption spectra. The effect of the alkyl chains length seems to play a minor role in the aggregation properties, as noticed by (1)H NMR data, optical absorption and fluorescence spectra, which remain almost unaltered on changing the chain length.     

A novel dinuclear Schiff-base copper(II) complex modified electrode for ascorbic acid catalytic oxidation and determination

A new dinuclear copper salicylaldehyde-glycine Schiff-base complex [Cu(2)(Sal-Gly)(2)(H(2)O)(2)] was synthesized and structurally characterized. [Cu(2)(Sal-Gly)(2)(H(2)O)(2)] crystallized in the monoclinic system in the P2(1)/c space group. The molecule is a dinuclear complex, formed by two [Cu(Sal-Gly)(H(2)O)] units. The electropolymerization properties of the copper complex on a glass carbon electrode were studied at different potential ranges. The electropolymerization occurred when the high scan potential reached 1.4 V. The modified electrode exhibited good electrocatalytic oxidation properties to ascorbic acid and showed a sensitivity of 22.9 nA μM(-1) (r(2) = 0.9998) and detection limit of 0.39 μM (S/N = 3) in the amperometric determination of ascorbic acid. The designed determination method can be used to analyze vitamin C tablets.     

Direct N-alkylation of amines with alcohols using AlCl_3 as a Lewis acid

A substitution reaction of amines with alcohols for N-alkylated amines has been developed using inexpensive AlCl_3 without any ligand or additive.Either aromatic or aliphatic amines and primary or secondary alcohols perform the AlCl_3-mediated reaction smoothly to afford various N-alkylated amines in satisfactory yields.     

Bis-dimethylaminobenzaldehyde Schiff-base cobalt(II) complex as a neutral carrier for a highly selective iodide electrode.

A new solvent polymeric membrane electrode based on N,N'-bis-(dimethylaminobenzaldehyde)-glycine cobalt(II) [Co(II)-BDMABG] as a neutral carrier is described, which displays a preferential potentiometric response to iodide ion and an anti-Hofmeister selectivity sequence in the following order: I- > ClO4- > Sal- > SCN- > NO2- > Br- > NO3- > Cl- > SO3(2-) > SO4(2-). The electrode exhibits a near-Nernstian potential linear range of 9.0 x 10(-7)-1.0 x 10(-1) M with a detection limit of 6.8 x 10(-7) M and a slope of -53.0 mV/decade in pH 2.0 of a phosphate buffer solution at 20 degrees C. The response mechanism is discussed in view of the A.C. impedance technique and the UV spectroscopy technique. The electrode was successfully applied to the determination of iodide in Jialing River and Spring in Jinyun Mountains with satisfactory results.     

Magnetic ordering in a mononuclear cobalt(II) complex containing a Schiff-base pentadentate ligand

A mononuclear cobalt(II) complex CoL5, containing the pentadentate O2N3 salen-type Schiff-base ligand H2L5=N,N[prime or minute]-bis(3-tert-butyl-2-hydroxy-5-methylbenzylidenyl)-1,7-diamino-4-methyl-4-azaheptane, exhibits magnetic ordering at 4 K as proven by ac magnetic susceptibility (both in- and out-of-phase), magnetization, field-cooled magnetization and zero-field cooled magnetization measurements.     

Investigation of chlorophylls as a scavenger of manganese(II) and zinc(II) using a radiotracer technique

Uptake of manganese(II) and zinc(II) by chlorophylla (Chl) was investigated using a radiotracer technique in order to elucidate its ability of scavenging metals released into the soil environment. Two possibilities were considered for the metal uptake: (1) substitutional complexation with Chl and (2) inclusion of the metals into Chl aggregates. It was found that manganese(II) was not trapped appreciably by both Chl itself and its aggregates. Magnesium of Chl was exchanged with zinc(II) in aqueous phase giving Zn−Chl at pH values higher than 7. Zinc(II) was found to be trapped by Chl aggregates depending on the pH of the aqueous phase.     

Heat effects of complex formation between maleic acid and zinc(II) and nickel(II) ions

The heat effects of formation of zinc(II) and nickel(II) complexes with maleic acid were determined by the direct calorimetric method at 298.15 K and several ionic strength values against the background of NaNO₃. The standard thermodynamic characteristics of complex formation in aqueous solution were calculated.     

Synthesis,characterization, and biological activity of a Schiff-base Zn(II) complex

Preparation and crystal structure of {4-chloro-2-[(2-morpholinoethylimino)methyl]phenolato} methanolchlorozinc(II) are reported. The X-ray structure reveals highly distorted square pyramidal geometry around zinc, binding to one phenolate O and two imine N atoms of the Schiff base, one methanol and one chloride. The complex and its ligand were tested in vitro for antibacterial and cytotoxic activity with a wide range of bactericidal activity and significant cytotoxic activity.     

Tin(IV) bis(perfluoroalkanesulfonyl)amide complex as a highly selective Lewis acid catalyst for Baeyer-Villiger oxidation using hydrogen peroxide in a fluorous recyclable phase

Sn[N(SO₂C₈F₁₇)₂]₄ catalyst was shown to give an excellent yield and selectivity in a fluorous biphasic catalytic system for Baeyer-Villiger oxidation of cyclic ketones by 35% aqueous hydrogen peroxide, a green, safe and cheap oxidant. Furthermore, the catalyst was completely recovered and reused in the fluorous immobilized phase without loss of activity.     

Compartmental Schiff-base ligands as selective double-loaded extractants for copper(II)

The Robson compartmental macrocyclic ligand derived from the condensation of derivatives of 2,6-diformylphenol and diamines has been prepared for the first time in its free ligand form; competitive three-phase transport and two-phase extraction studies confirm high double-loaded selectivity for the binding and delivery of Cu(II).     

Cobalt(II), nickel(II) and zinc(II) coordination compounds derived from aromatic amines

The structural and spectroscopic characterization of coordination compounds of four aromatic amines derived from benzimidazole, 2-aminobenzimidazole (L1), 1-(S-methylcarbodithioate)-2-aminobenzimidazole (L2), 2-(2-aminophenyl)-1H-benzimidazole (L3) and 6,6-dimethyl-5H-benzimidazolyl[1,2-c]quinazoline (L4) are reported. Cobalt(II) [Co(L1)₂(CH₃COO)₂] (1) and nickel(II) [Ni(L1)₂(CH₃COO)₂] (2) acetate coordination compounds of L1 are discussed. The synthesis and the X-ray crystal structure of the new 1-(S-methylcarbodithioate)-2-aminobenzimidazole (L2) is informed, together with its cobalt(II) [Co(L2)₂Cl₂] (3), [Co(L2)₂Br₂] (4) and zinc(II) [Co(L2)₂Cl₂] (5), [Zn(L2)₂Br₂] (6) coordination compounds. In these compounds the imidazolic nitrogen is coordinated to the metal center, while the ArNH₂ and the S-methylcarbodithioate groups do not participate as coordination sites. A co-crystal of L1 and L2 is analyzed. Structural analyses of the coordination compounds of L3 showed that this ligand behaves as a bidentate ligand through the aniline and the imidazole groups forming six membered rings in the cobalt(II) [Co(L3)Cl₂] (7) and zinc(II) [Zn(L3)Cl₂] (8) compounds, as well as the nickel(II) nitrate [Ni(L3)₂(H₂O)₂](NO₃)₂ (9). The quinazoline L4 was produced by insertion of one acetone molecule and water elimination in L3, its X-ray crystal diffraction analysis, as well as that of its zinc(II) coordination compound [Zn(L4)₂Cl₂] (10), are discussed.     

Synthesis and characterization of biocompatible poly (L-lactide) using zinc (II) salen complex

Abstract

A biocompatible zinc (II) complex based on a tetradentate N,N,O,O-type salen ligand was synthesized, characterized and used for the solvent-free ring-opening polymerization (ROP) of L-lactide in bulk at 180?°C to prepare high molecular weight poly(L-lactide) (M_n : 82,600?Da; M_w : 140,000?Da; PDI: 1.70). Poly(L-lactide) (PLLA) was characterized using FTIR, ¹H NMR, ¹³C NMR, GPC, TGA, DSC, WAXD, and MALDI-ToF. Kinetic measurement was carried out and first-order behavior to monomer was observed. The k _app was found as 6?±?0.001?×?10^?4?s^?1. The biocompatibility of the PLLA was confirmed by in vitro cytotoxicity against NIH/3T3 fibroblast cell line and can be used in biomedical applications.     

Electrochemical investigations on pentagonal bipyramidal complexes of manganese(II), iron(II), and cobalt(II) with a heptadentate Schiff-base ligand in non-aqueous solvents

Summary The voltammetric properties of the complexes formed by manganese(II), iron(II), and cobalt(II) ions with a heptadentate Schiff-base ligand have been investigated by cyclic voltammetry and controlled-potential coulometry at mercury and platinum electrodes in acetonitrile and dimethyl sulfoxide solvents.All the species undergo a single one-electron oxidation process leading to the corresponding stable metal(III) complexes which have been isolated and characterized.The cathodic behaviour of manganese(II) and iron(II) derivatives is very similar, in that the less cathodic process occurs at nearly equal potential values, indicating that the ligand moiety is reduced rather than the metal centre. The one-electron reduction process of the cobalt(II) complex leads to the corresponding cobalt(I) derivative, stable in the electrolysis solution.