Activation of peroxyl and molecular oxygen using bis -benzimidazole diamide copper (II) compounds

New tetradentatebis-benzimidazole ligands have been synthesized and utilized to prepare copper (II) complexes. Some of these copper (II) complexes have been characterized structurally. The copper (II) in these complexes is found to possess varying geometries. A distorted octahedral geometry is found with a highly unsymmetrical bidentate nitrate group. An unusual polymeric one-dimensional structure is observed where copper (II) is in a distorted square pyramidal geometry with a monodentate nitrate ion, having long Cu-O bond, while a distorted triagonal bipyramidal geometry is found with two carbonyl O atoms and a Cl atom in the equatorial plane, and two benzimidazole imine N atoms occupy the axial position. These compounds are found to activate the cumylperoxyl group, and this has been utilized in the facile oxidation of aromatic alcohols to aldehydes, where they act as catalysts with large turnovers. The yields of the respective products vary from 32 to 65%. The role of molecular oxygen has been studied and an attempt has been made to identify the “active copper species”. Activation of molecular oxygen has also been observed and has been used for oxidative dealkylation of a hindered phenol, producing di-butyl quinones with yields of 20–25% and 10–12 fold catalytic turnover. Dihydroxybenzenes and substituted catechols are also readily oxidized to the corresponding quinones, in oxygen-saturated solvents. Yields of 84% have been observed with 34-fold catalyst turnover, with di-t-butylcatechol. The activity of these copper (II) —bis-benzmidazolediamide compounds is reminiscent of the functioning of copper centres in galactose oxidase, tyrosinase and catechol oxidase.     

Systematic investigations of the multi-element preconcentration from copper by precipitation of the matrix as copper(I) oxide and copper(I) thiocyanate

Two methods for multi-element preconcentration from copper by reductive matrix precipitation are presented. In systematic investigations on the coprecipitation behaviour of Ag, Al, Au, Bi, Cd, Co, Cr, Fe, Ga, In, Mn, Mo, NJ, Pb, Sb, Se, Sn, Te and Zn during precipitation of the copper matrix as Cu₂O or CuSCN, the separation parameters were optimized. By combination with a hexamethyleneammonium hexamethylenedithiocarbamate collector precipitation, a concentration of 8 elements (Cu₂O precipitation) or 13 elements (CuSCN precipitation) in a small volume was achieved. The limits of detection of the procedures are, depending on the element, 0.1–5 μg g^?1 for flame atomic absorption spectrometry (AAS) and 0.01–0.1 μg g^?1 for graphite furnace AAS. The relative standard deviations are about 3%. The analytical performance of the procedures is compared with that of an electrolytic copper separation.     

Laser induced copper electroless plating on polyimide with Q-switch Nd:YAG laser

The results of laser induced deposition of copper on polyimide substrate from copper electrolyte solution are reported. Unlike most work reported in the literatures where CW Ar⁺ lasers were used, a second harmonic (532 nm wavelength) Q-switch Nd:YAG laser was used for our experiments. The deposition process was conducted by laser-catalyzing of the polyimide surface and subsequent photothermal-accelerated reduction of copper-complex ions in an alkaline reducing environment. The characteristics of the deposited copper line were investigated in terms of laser beam scanning speed, and the number of scans. The surface morphology and chemical composition of the deposited copper were analyzed using field emission scanning electron microscope (FESEM) and energy dispersive spectrometer (EDX). The optimum processing conditions have been identified. The copper deposit was found to adhere well to the substrate.     

Conjugate addition of pyrroles to α,β-unsaturated ketones using copper bromide as a catalyst

Copper bromide was used as a catalyst for the addition of pyrroles to enones. When both the reactants were used in equimolar amounts, mono and dialkylated products were obtained. However, the use of excess enone furnished only dialkylated products. Thus, copper bromide was shown to be an efficient catalyst for the dialkylation of pyrroles.     

Influence of the Type of a Ligand on the Intensity of Luminescence of Ln3+ Ions in Aqueous Solutions

The luminescence characteristics of hydrated Ln³⁺ ions and their complexes with some acidic ligands have been investigated. The possibility of determining the stability of the complexes of lanthanides in solutions from the intensity of luminescence bands is shown. The influence of the characteristic features of the f-electron shell of Ln³⁺ on the formation of the spectrochemical series is discussed.     

Initial oxidation kinetics of copper (1 1 0) film investigated by in situ UHV-TEM

Previous studies of the initial stage of oxidation on clean single crystal of Cu(1 0 0) have been extended to the case of the Cu(1 1 0) surface. The dynamic observation of the nucleation and growth of Cu oxide by means of in situ ultra high vacuum transmission electron microscopy (UHV-TEM) shows a highly enhanced oxidation rate on Cu(1 1 0) surface as compared to Cu(1 0 0). The kinetic data on the nucleation and growth of the three-dimensional oxide islands agree well with our heteroepitaxial model of surface diffusion of oxygen.     

Stationary entanglement between macroscopic mechanical oscillators

We show that the optomechanical coupling between an optical cavity mode and two movable cavity mirrors is able to entangle two different macroscopic oscillation modes of the mirrors. This continuous variable entanglement is maintained by the light bouncing between the mirrors and is robust against thermal noise. In fact, it could be experimentally demonstrated using present technology. Received 2 September 2002 / Received in final form 10 October 2002 Published online 7 January 2003     

Radial and angular correlation in heliumlike ions

In the framework of nonrelativistic variational formalism a new type of basis set is proposed, to estimate separately the effect of radial and angular correlations on the ground‐state energy for helium isoelectronic sequence H^? to Ar¹⁶⁺. Effect of radial correlation is incorporated by using multiexponential functions arising from product basis sets suitably formed out of Slater‐type one‐particle orbitals. The angular correlation can be switched on by incorporating an expansion in terms of basis involving interparticle coordinates. With a set of six‐term Slater‐type one‐particle basis and five‐term interparticle expansion, the ground‐state energy of helium is estimated as ?2.9037236 (a.u.) compared with the multiterm variational estimates ?2.9037244 (a.u.) due to Pekeris and Thakkar and Smith and Drake. Matrix elements of different operators in the ground state have been calculated and found to be in good agreement with available accurate results. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003     

EQCM Study of the Couple Thallium(I)/Thallium Amalgam at a Thin Film Mercury Electrode

EQCM and voltammetric data show that thallium(I) ions, which are adsorbed in the region of the positive surface charge, most probably, in the form of the ionic pairs, are not reduced. In this potential region, thallium(I) ions are reduced directly from the solution. At more negative potentials, the previously adsorbed stable ionic pairs slowly undergo transition into the less stable form. From this form, thallium(I) ions can be reduced or desorbed into the solution. The process is best described by a model of one electron, i.e., full charge transfer.