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.     

Crystallographic report: A new polymorph for bis[bis(N,N‐dibenzyldithiocarbamato)cadmium(II)]

The title compound is a centrosymmetric dimer with each cadmium in a distorted CdS₅ square pyramidal geometry. The Cd–S bond distances range from 2.5626(11) to 2.8459(11) Å. Copyright © 2004 John Wiley & Sons, Ltd.     

Thermal behavior of metallodendrimers possessing bis(terpyridinyl)Ru(II) connectivity and different surface functionality

A series of metallodendrimers, assembled by means of bis(terpyridinyl)Ru^(II) connectivity on poly(propylene imine) dendrimer scaffolds, with homogeneous or heterogeneous surfaces, were prepared. Differential scanning calorimetry and thermogravimetric analysis were used to determine their thermal behavior, glass‐transition temperatures, and the decomposition kinetics and temperatures; no synergy effects for these properties were observed for the heterogeneously surfaced constructs in contrast to the corresponding homogeneously coated materials, which exhibited different values depending on their surface functionalities. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1487–1495, 2004     

Kinetic features of ethylene polymerization over supported catalysts [2,6‐bis(imino)pyridyl iron dichloride/magnesium dichloride] with AlR3 as an activator

The effects of polymerization temperature, polymerization time, ethylene and hydrogen concentration, and effect of comonomers (hexene‐1, propylene) on the activity of supported catalyst of composition LFeCl₂/MgCl₂‐Al(i‐Bu)₃ (L = 2,6‐bis[1‐(2,6‐dimethylphenylimino)ethyl] pyridyl) and polymer characteristics (molecular weight (MW), molecular‐weight distribution (MWD), molecular structure) have been studied. Effective activation energy of ethylene polymerization over LFeCl₂/MgCl₂‐Al(i‐Bu)₃ has a value typical of supported Ziegler–Natta catalysts (11.9 kcal/mol). The polymerization reaction is of the first order with respect to monomer at the ethylene concentration >0.2 mol/L. Addition of small amounts of hydrogen (9–17%) significantly increases the activity; however, further increase in hydrogen concentration decreases the activity. The IRS and DSC analysis of PE indicates that catalyst LFeCl₂/MgCl₂‐Al(i‐Bu)₃ has a very low copolymerizing ability toward propylene and hexene‐1. MW and MWD of PE produced over these catalysts depend on the polymerization time, ethylene and hexene‐1 concentration. The activation effect of hydrogen and other kinetic features of ethylene polymerization over supported catalysts based on the Fe (II) complexes are discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5057–5066, 2007     

Crystallographic report: Bis[bis(N,N‐dibenzyldithiocarbamato)cadmium(II)]

The centrosymmetric structure of {Cd[S₂CN(CH₂Ph)₂]₂}₂ features both bridging and chelating dithiocarbamate ligands so that a square pyramidal S₅ coordination geometry results. Copyright © 2004 John Wiley & Sons, Ltd.     

NMR studies on a palladium(II) complex containing an incompletely coordinated facultative pentadentate Schiff base ligand

Palladium(II) dichloride reacts with 1,10‐bis(2‐pyrrolyl)‐2,5,9‐triaza‐1,9‐decadiene to give a [Pd(C₁₅H₂₀N₅)]Cl complex in which the ligand is four‐coordinated, leaving one pyrrole group dangling. By using COSY, gHSQC, gHMBC connectivities and NOE experiments it has been concluded that one linkage isomer exists in DMSO solution, in spite of the fact that different sets of N atoms of potentially pentadentate ligand might be involved in coordination, and that the three chelate rings in the complex cation are arranged in a sequence: five‐membered, six‐membered, five‐membered which is different from that (5–5–6) found by x‐ray studies on the related [Ni(C₁₅H₂₀N₅)]Cl compound. NMR studies allowed an unambiguous assignment of all ¹H and ¹³C NMR resonances for the complex. Results of x‐ray structural analysis of [Pd(C₁₅H₂₀N₅)](CH₃COO)H₂O supported the five‐membered, six‐membered, five‐membered ring sequence in the [Pd(C₁₅H₂₀N₅)]⁺ complex cation and show an E (trans) orientation of the dangling pyrrole group with respect to the metal center. Copyright © 2002 John Wiley & Sons, Ltd.     

Breakage of λ-DNA by inorganic tin and organotin compounds as environmental pollutants

In proportion to the environmental pollution problems caused by organotin compounds, the genotoxicities of tin compounds in the environments have become of interest so as to estimate their safety in recent years. In this work, isolated λ-DNA (double-strand DNA) was incubated with inorganic tin(II) and tin(IV) and five organotin compounds [n-butyltin trichloride, di(n-butyltin) dichloride, methyltin trichloride, dimethyltin dichloride and trimethyltin chloride] in reaction systems both with and without hydrogen peroxide (H₂O₂) content. The tin compounds tested in this study did not induce DNA breakage in the absence of hydrogen peroxide. Divalent inorganic tin (SnCl₂) and tetravalent inorganic tin (SnCl₄) caused DNA breakage in the presence of hydrogen peroxide (10 mM), and the DNA damage activity of inorganic tin was much more potent in divalent inorganic tin (SnCl₂) than in tetravalent inorganic tin (SnCl₄). Divalent inorganic tin (SnCl₂) induced DNA breakage in a concentration-dependent fashion at concentrations greater than 0.1 mM of SnCl₂ in the presence of hydrogen peroxide (10 mM). DNA breakage was not caused by n-butyltin compounds and methyltin compounds either in the presence or in the absence of hydrogen peroxide.     

Metal complexation of crosslinked polyacrylamide-supported dithiocarbamates: Effect of the molecular character and extent of crosslinking on complexation

Dithiocarbamate functions were incorporated into different polyacrylamide matrices crosslinked with a flexible and hydrophilic crosslinking agent, tetraethyleneglycol diacrylate (TEGDA), and their complexation behaviours were investigated. Crosslinked polyacrylamides with varying extents of the tetrafunctional TEGDA crosslinks were prepared by free radical solution polymerization at 60°C using potassium persulphate as initiator in ethanol. The dithiocarbamate functionality was incorporated into these polyacrylamides by a two-step polymer-analogous reaction involving (i)trans-amidation with ethylenediamine and (ii) dithiocarbamylation of the aminopolyacrylamide with carbon disulphide and alkali. The complexations of dithiocarbamate with Cu(II), Ni(II), Zn(II), Co(II) and Hg(II) ions were followed under different conditions. The metal ion intake varied with the extent of the crosslinking agent and the observed trend in complexation is Hg(II) > Cu(II)> Zn(II)> Co(II)> Ni (II). The time-course of complexation, the possibility of recycling, swelling characteristics, and spectral and thermal analyses were carried out. The thermal stability increases upon complexation with metal ions.     

Pd (II)‐catalyzed vinyl addition polymerization of novel functionalized norbornene bearing dimethyl carboxylate groups

Three novel functionalized polynorbornenes (PNB) with pendant dimethyl carboxylate group (carboxylates—acetate, propionate, and butyrate) are synthesized as a vinyl‐type with a palladium (II) catalyst in high yield. The effects of size of substitutents, molar ratio of monomer to catalyst, solvent polarity, reaction time, and temperature on the polymerization of exo‐norbornene dimethyl propionate were systematically investigated. The low molar ratio and temperature, as well as high polarity of solvent, and long reaction time, are favorable for the enhancement of the monomer conversion, especially, the solvent have an obvious effect on the catalyst activity. The resulting poly(cis‐norbornene‐exo‐2,3‐dimethyl carboxylates) (PNB‐dimethyl carboxylates) show good solubility in common organic solvent and high thermal stability up to 360 °C. The glass transition temperature was detected by DMA at 331, 324, and 318 °C for acetate, propionate, and butyrate, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3391–3399, 2007     

四磺酸基酞菁锌在水和非水溶剂中的电化学性质研究

在非水溶剂（二甲基亚砜（ＤＭＳＯ）及Ｎ,Ｎ＿二甲基甲酰胺（ＤＭＦ））中的伏安曲线．呈现三对电流峰,表明存在三个可逆或准可逆酞菁配体的单电子转移过程,而在水溶液中则不呈现准可逆行为,且波形改变很大．此外,还比较了四磺酸基酞菁锌的水溶液在自然光和红光（６００～７００ｎｍ）照射下的循环伏安曲线,其氧化还原峰的数目和峰电位基本不变,但在红光照射下比自然光照射下的峰电流明显增大．