A new series of dinucleating macrocyclic ligands and their complexes of zinc(II)

A new category of dinucleating macrocyclic Schiff base ligands with ring sizes from 34- to 52-membered have been synthesised employing metal template procedures involving the reaction of o-phenylenediamine with a series of α,ω-bis(3′-hydroxy-4′-formylphenyloxy)alkanes in the presence of calcium(II), barium(II) or manganese(II). The latter cations act as ‘transient’ templates for formation of the corresponding metal-free Schiff base macrocyclic ligands, H₄Lⁿ (where n signifies the number of carbons in each linking bis-alkoxy chain); the macrocycles corresponding to n = 4, 6 and 8 were isolated and characterised while, for n = 1, in which single methylene groups acts as the bridges between salicyl moieties, the cyclic product was used directly for preparation of its dinuclear complex, [Zn₂L¹], without prior isolation. Evidence for the templating role of barium in the preparation of H₄L⁶ and H₄L⁸ was obtained by isolation of the corresponding species of type H₄Lⁿ·2Ba(ClO₄)₂ (n = 6 or 8) as ‘intermediates’ before generation of the respective metal-free macrocycles. Reaction of zinc(II) acetate with the free macrocycles in methanol yielded complexes of type [Zn₂Lⁿ] in all cases. A related non-cyclic ligand, H₂L⁰ and its corresponding mononuclear complex, [ZnL⁰]·H₂O, were also synthesised and its spectral properties compared with those of the macrocyclic derivatives. The elemental analyses, ¹H NMR, IR, UV–Vis and MS spectra of the respective zinc complexes in each case were in accord with the formation of the expected 2:2 condensation product. The results of DFT calculations to probe aspects of the electronic and structural natures of both H₂L¹ and H₄L⁴ are briefly presented.     

Ferromagnetic exchange coupling in phosphonato-bridged dinuclear copper(II) compound with monoethyl (pyridyn-2-ylmethyl)phosphonate ligand (2-mpmpe): Cu2(2-mpmpe)2(H2O)2(NO3)2

The interaction of diethyl (pyridyn-2-ylmethyl)phosphonate (2-pmpe) with Cu(NO₃)₂ · 6H₂O leads to a partial hydrolysis of the starting ligand and formation of the compound of the formula Cu₂(2-mpmpe)₂(H₂O)₂(NO₃)₂, where 2-mpmpe = monoethyl (pyridyn-2-ylmethyl)phosphonate. The crystal and molecular structure of a copper(II) compound was determined by single X-ray diffraction method. Its structure consists of five-coordinated in distorted square planar geometry (CuNO₄ chromophore) copper(II) ions doubly bridged by OPO from phosphonate. The Cu?Cu distance is 4.69 Å. The crystal packing is determined by the interdinuclear hydrogen bond system, which leads to a three-dimensional (3D) H-bonds network. The compound was characterized by infrared, ligand field, EPR spectroscopy, and magnetic studies. The magnetic properties of the title compound investigated over the 1.8–300 K, revealed the occurrence of a weak ferromagnetic coupling through phosphonate bridge (J = 1.86 cm⁻¹) and interdimer superexchange coupling through H-bond network (zJ′ = −0.17 cm⁻¹). Spectroscopic and magnetic properties are presented in the light of crystal structure.     

Structural,theoretical and multinuclear NMR study of mercury(II) complexes of phosphorus ylides: Mono and binuclear complexes

Reaction of phosphorus ylide Ph₃PCHC(O)C₆H₄Cl (Y₁) with HgX₂ (X = Cl, Br and I) and ylide (p-tolyl)₃PCHC(O)CH₃ (Y₂) with HgI₂ in equimolar ratios using methanol as solvent leads to binuclear products. The bridge-splitting reaction of binuclear complex [(Y₁) · HgCl₂]₂ by DMSO yields a mononuclear complex containing DMSO as ligand. O-coordination of DMSO is revealed by single crystal X-ray analysis in mononuclear complex of [(Y₁) · HgCl₂ · DMSO]. C-coordination of ylides is confirmed by X-ray structure of binuclear complex [(Y₂) · HgI₂]₂. Characterization of the obtained compounds was also performed by elemental analysis, IR, ¹H, ³¹P, and ¹³C NMR. Theoretical studies on mercury(II) complexes of Y₁ show that formation of mononuclear complexes in DMSO solution in which DMSO acts as a ligand, energetically is more favorable than that of binuclear complexes.     

Pd(II)/Lewis Acid Catalyzed Intramolecular Oxidative C−H Amination to Construct Carbazoles with Dioxygen

Transition-metal-catalyzed oxidative C−H amination reactions are among the most attractive topics in organic synthesis to construct nitrogen-containing motifs. The challenge is that most of these reactions employed stoichiometric oxidants to achieve satisfied catalytic efficiencies. Herein, we report a Pd(II)/LA-catalyzed (LA: Lewis acid) oxidative C−H amination reaction of 2-acetaminobiphenyls to construct carbazoles by using dioxygen balloon as the sole oxidant source, and the presence of LA sharply improved the catalytic efficiency of Pd(OAc)₂. Remarkably, in certain cases, the deacetylation of the annulation product happened under standard conditions to afford free carbazoles as the final product. The H/D exchange studies confirmed the reversibility of C−H activation and also disclosed multiple C−H activation sites by using −NAc and −NTs as the directing groups. In addition, the palladacycle compound was identified through ¹H NMR characterizations and proved to be the intermediate prior to the carbazole formation.     

A fluorescent chemosensor for cobalt ions based on a multi-substituted phenol-ruthenium(II) tris(bipyridine) complex

An amide-linked 2,6-bis{[(2-hydroxy-5-tert-butylbenzyl)(pyridyl-2-methyl)-amino]-methyl}-4-methylphenol-ruthenium(II) tris(bipyridine) 2PF₆⁻ complex, 1, was first used to recognize Co(II) in EtOH/H₂O (1:1, v/v) solution, with the ruthenium(II) tris(bipyridine) moiety selected as a fluorophore and the multi-substituted phenol unit chosen as a receptor. The fluorescence quenching of 1 was attributed to the formation of an inclusion complex between multi-substituted phenol unit and Co(II) by 1:1 complex ratio (K = 2.5 × 10⁵), which has been utilized as the basis of the fabrication of the Co(II)-sensitive fluorescent chemosensor. The analytical performance characteristics of the proposed Co(II)-sensitive chemosensor were investigated. The sensor can be applied to the quantification of Co(II) with a linear range covering from 1.0 × 10⁻⁷ to 5.0 × 10⁻⁵ M and a detection limit of 5 × 10⁻⁸ M. The experiment results show that the response behavior of 1 to Co(II) is pH-independent in medium condition (pH 4.5–9.5) and show excellent selectivity for Co(II) over transition metal cations except Cu(II). The chemosensor has been used for determination of Co(II) in water samples.     

Reactivity of triazolyl Schiff bases with Ru(II)-2,2′-bipyridyl: Synthesis,spectroscopic characterization of isomers and their photo-physical properties

The condensation of 3-amino-1H-1,2,4-triazole with benzaldehyde and terephthalaldehyde provides the bidentate and tetradentate Schiff bases 1,2,4-triazolo-3-imino-benzene L¹H and 1,4-bis(1,2,4-triazolo-3-imino)benzene L²H₂, respectively. The well characterized Schiff bases were allowed to react with cis-Ru(bpy)₂Cl₂ · 2H₂O. Isomers of the mononuclear complexes Ru(bpy)₂L¹]PF₆ · NH₄PF₆ (1a, N4) and [Ru(bpy)₂L¹]PF₆ · 0.5NH₄PF₆ (1b, N2), and the dinuclear Ru(II) complexes [Ru(bpy)₂L²Ru(bpy)₂](PF₆)₂ · NH₄PF₆ (2a, N4N4), [Ru(bpy)₂L²Ru(bpy)₂](PF₆)₂ · NH₄PF₆ · 2H₂O (2b, N2N2) and [Ru(bpy)₂L²Ru(bpy)₂](PF₆)₃ · NH₄PF₆ (2c, Ru(II)-Ru(III)) were separated by column chromatography and characterized by their elemental analysis, FAB mass and spectral (IR, NMR, UV–Vis) data. The data obtained suggest that the ligands are bound to the metal centre via the N4 and N2 atoms of the triazole moiety along with the N (imine) atom. The complexes display metal-to-ligand charge-transfer (MLCT) transitions in the visible region from the dπ(Ru^II) → π^∗L transition. Highly intense ligand-based π→π^∗ transitions are observed in the UV region. A dual emission occurs from the N2 and N2N2 isomers.     

A novel tris(2,2′-bipyridine)ruthenium(II)/tripropylamine cathodic electrochemiluminescence in acetonitrile for the indirect determination of hydrogen peroxide

A novel tris(2,2′-bipyridine)ruthenium(II) (Ru(bpy)₃²⁺) cathodic electrochemiluminescence (ECL) was generated at −0.78 V at the Pt electrode in acetonitrile (ACN), which suggested that the cathodic ECL differed from conventional cathodic ECL. It was found that tripropylamine (TPrA) could enhance this cathodic ECL and the linear range (log-log plot) was 0.2 μM-0.2 mM. In addition, hydrogen peroxide (H₂O₂) could inhibit the cathodic ECL and was indirectly detected with the linear range of 27-540 μM. The RSD (n = 12) of the ECL intensity in the presence of 135 μM H₂O₂ was 0.87%. This method was also demonstrated for the fast determination of H₂O₂ in disinfectant sample and satisfactory results were obtained.     

Fluorescence sensing of Cu within a pseudo 18-crown-6 cavity

We report herein a pseudo-crown based fluorescent receptor (1) for the selective detection of Cu²⁺ cation. Receptor 1 can detect Cu²⁺ even in 5 μM level in acetonitrile-water (9:1 v/v). Compound 1 is very effective for the detection of Cu²⁺ amongst the series of metal ions studied (Li⁺, Na⁺, K⁺, Ca²⁺, Mg²⁺, Ba²⁺, Pb²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺ and Mn²⁺).     

Reduction kinetics of glycinate complexes of palladium(II) on a dropping-mercury electrode in acid perchlorate solutions

Polarograms for the reduction of glycinate complexes of palladium(II) (5 × 10^?5 M) are obtained in equilibrium solutions of pH 0.8–3.0 with different protonated-glycine concentrations c _Hgly (supporting electrolyte, 0.5 M NaClO₄). It is established that the irreversible wave of reduction of complexes Pd(gly)₂ corresponds to the diffusion limiting current I _d ⁽²⁾ . A similar wave at pH 1.5 and c _Hgly = 0.005 M, as well as at pH 1.0 and c _Hgly = 0.05–0.5 M is preceded by the diffusion limiting current I _d ⁽¹⁾ . Values of the I _d ⁽²⁾ /I _d ⁽¹⁾ ratio are close to the ratio between equilibrium concentrations of Pd(gly)₂] and [Pdgly⁺], calculated using the step stability constant for Pd(gly)₂. This fact testifies to the reduction of complexes Pdgly⁺ in the vicinity of I _d ⁽¹⁾ and complexes Pd(gly)₂, in the vicinity of I _d ⁽²⁾ . At pH 0.8–1.2 and [H₂gly⁺] = 1 × 10^?4 to 5 × 10^?3 there is observed the diffusion-kinetic limiting current of the first wave I ₁ ⁽¹⁾ , which increases with increasing [H⁺] and decreasing [H₂gly⁺]. The nature of the slow preceding chemical stage that occurs during the reduction of complexes Pdgly⁺ is discussed.     

Thermal decomposition of copper(II) and zinc carbonate hydroxides by means of TG-MS

Summary For the quantitative analyses of evolved CO₂and H₂O during the thermal decomposition of solids, calibration curves, i.e. the amounts of evolved gases vs. the corresponding peak areas of mass chromatograms measured by TG-MS, were plotted as referenced by the reaction stoichiometry of the thermal decomposition of sodium hydrogencarbonate NaHCO₃. The accuracy and reliability of the quantitative analyses of the evolved CO₂and H₂O based on the calibration curves were evaluated by applying the calibration curves to the mass chromatograms for the thermal decompositions of copper(II) and zinc carbonate hydroxides. It was indicated from the observed ratio of evolved CO₂and H₂O that the compositions of copper(II) and zinc carbonate hydroxides examined in this study correspond to mineral malachite, Cu₂CO₃(OH)₂, and hydrozincate, Zn₅(CO₃)₂(OH)₆, respectively. Reliability of the present analytical procedure was confirmed by the fairly good agreement of the mass fraction of the evolved gases calculated from the analytical values with the total mass-loss during the thermal decompositions measured by TG.