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1.
Pavan Mathur 《Journal of Chemical Sciences》2006,118(6):553-568
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. 相似文献
2.
Seok‐Ho Hwang Kyung Soo Yoo Charles N. Moorefield Sang‐Won Lee George R. Newkome 《Journal of Polymer Science.Polymer Physics》2004,42(8):1487-1495
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 相似文献
3.
Tatiana B. Mikenas Vladimir A. Zakharov Lyudmila G. Echevskaya Mikhail A. Matsko 《Journal of polymer science. Part A, Polymer chemistry》2007,45(22):5057-5066
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 相似文献
4.
If g and G are the pdf and the cdf of a distribution symmetric around 0 then the pdf 2g(u)G(λ
u) is said to define a skew distribution. In this paper, we provide a mathematical treatment of the skew distributions when
g and G are taken to come from one of Pearson type II, Pearson type VII or the generalized t distribution.
相似文献
5.
M. C. Jones 《Annals of the Institute of Statistical Mathematics》2004,56(4):733-742
A simple new family of distributions is proposed which has support the unit disc in two dimensions. The density functions
of the family are unimodal, monotonic or uniantimodal. The bivariate symmetric beta distributions, which include the uniform
distribution, are special cases, but many members of the family are skew. The distributions have three parameters, one controlling
orientation, one controlling degree of concentration and the third controlling skewness, or more precisely off-centredness.
Importantly, these parameters are globally orthogonal. An illustrative example of fitting the model to data is given. Conditional
and marginal distributions are considered. The new distributions are compared favourably with an earlier suggestion of the
same author. 相似文献
6.
《Magnetic resonance in chemistry : MRC》2003,41(1):61-64
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. 相似文献
7.
DEBACHE Abdelmadjid BOULCINA Raouf TAFER Radia BELFAITAH Ali RHOUATI Salah CARBONI Bertrand 《中国化学》2008,26(11):2112-2116
The synthesis of 1,2,3,4-dihydropyrimidinone/thione derivatives was achieved in good to excellent yields using calcium(II) nitrate as catalyst to promote the Biginelli three-component condensation reaction from a diversity of aromatic aldehydes, β-keto compounds and urea or thiourea. The reaction was carried out under solvent-free conditions. 相似文献
8.
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. 相似文献
9.
We have used electronic spectroscopy in the 160–1100 nm range to study the polyvinyl alcohol-nickel(II) chloride system. Based
on the results obtained, we hypothesize formation of mixed-ligand complexes of the type [Ni(H2O)6-nCln]2-n (n = 0, 1,..., 5) in the polyvinyl alcohol matrix. Transformation of the coordination sphere as the NiCl2 concentration changes is apparent both in the region of the d-d transition bands (350–1100 nm) and in the region of the charge
transfer bands (160–250 nm). We propose assigning the absorption bands separated by mathematical treatment to complexes of
specific compositions.
__________
Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 1, pp. 136–138, January–February, 2006. 相似文献
10.
Binyuan Liu Yang Li Boo‐Gyo Shin Do Yeung Yoon IL Kim Li Zhang Weidong Yan 《Journal of polymer science. Part A, Polymer chemistry》2007,45(15):3391-3399
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 相似文献