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1.
The novel binucleating ligand, 6,6 prime-methylene-bis(5 prime-amino-3 prime,4 prime-benzo-2 prime-thiapentyl)-1,11-diamino-2,3:9,10-dibenzo-4,8-dithiaundecane
(H4L) was prepared and reacted with copper(II) salts in dry MeOH to yield mixtures of copper(I) and copper(II) complexes with
Cl- and ClO-4 counter ions. The amine functions on the ligand release protons to form copper(I) complexes: (Cu2L)X2, where
X=Cl−, ClO4-. The complexes were oxidized to (Cu2L)X4 with H2O2 in DMF; Cu(NO3)2 gave a different complex, [Cu2(H4L)(NO3)2](NO3)2,
as regards proton releasing ability, coordination and oxidation number. Evidence for the structures of this new tetraamino-tetrathioether
ligand and its copper complexes is provided by 1H-, 13C-n.m.r., mass, u.v.–vis., i.r. spectra, elemental analyses, molar conductivities
and magnetic moments.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
2.
Serdar Karabcek Ismail Degirmencioglu Nevin Karabcek Mustafa Er Kerim Serbest 《Journal of heterocyclic chemistry》2003,40(4):639-643
The synthesis and structural properties of three novel imidates, 11,13‐bis‐(2‐amino‐ethylimino)‐1,10‐dioxa‐4,7‐dithiacyclotridecane ( 2 ), 11,13‐bis‐(3‐aminopropylimino)‐1,10‐dioxa‐4,7‐dithiacyclotridecane, ( 3 ) and 2,11‐dioxa‐5,8‐dithia‐13,16,19,22‐tetraazabicyclo[10.10.1]tricosa‐1(22),12‐diene, ( 4 ) have been described. These compounds were synthesized by treating 1,10‐dioxa‐4,7‐dithiacyclotridecane‐11,13‐diester ( 1 ) with the appropriate diamine under N2 and their structures have been characterised by elemental analyses, 1H‐ and 13C‐nmr, ir, and mass spectral studies. Elemental analyses and spectroscopic data support the proposed imidate structures. In addition, total energy and heat of formation (Figure 2) calculated for imidates 2a‐4a and 2b‐4b by the semiempirical AM1 calculations have shown that imidates 2b‐4b having intramolecular hydrogen bonds are more stable (5‐10 kcal/mol) than compounds 2a‐4a . 相似文献
3.
Nagihan Saglam Ahmet Colak Kerim Serbest Serdar Karab?cek Saadettin Güner 《Monatshefte für Chemie / Chemical Monthly》2004,15(4):1023-1031
Nucleolytic activities of novel mononuclear Cu(II), homo- and heterodinuclear Cu(II)–Ni(II) complexes with two diester-type ligands were investigated on pCYTEXP by neutral agarose gel electrophoresis. The analyses of the cleavage products obtained electrophoretically indicate that the examined complexes induce very similar conformational changes on supercoiled DNA by converting supercoiled form to nicked form. At concentrations greater than 100M, the complexes possessed effective nucleolytic activities for 10min of incubation time. However, their nucleolytic activities did not increase significantly with longer periods of incubation. The pH-nucleolytic activity profiles of the complexes differed significantly. Metal complex induced DNA cleavage was also tested for inhibition by various radical scavengers. It could be proposed from the data that diffusible intermediate oxidants are not involved in these reactions or they are not necessary for DNA cleavage since none of antioxidants inhibited DNA cleaving activities of the complexes. 相似文献
4.
M. S. Platz W. R. White D. A. Modarelli S. Celebi 《Research on Chemical Intermediates》1994,20(2):175-193
The photochemistry of diazirines and diazo compounds is not as simple as nitrogen extrusion and carbene formation. The C-H
bonds adjacent to the diazo and diazirine moieties can migrate in the excited state and produce stable products without the
benefit of a relaxed carbene intermediate. Additionally, cyclobutyl substituted systems exhibit carbon migration. It is unfortunate
that the products of photochemical rearrangement of precursor excited states are identical to the products of thermal rearrangement
of carbenes. This has prevented accurate measurement of the yield and absolute reactivity of alkylcarbenes. That pyridine
reacts selectively with carbenes and not with the excited states of their nitrogenous precursors has allowed the separation
of these two pathways and an appreciation of their relative importance with structural variation. 相似文献
5.
Serdar S. Celebi Gow-Jen Tsai George T. Tsao 《Applied biochemistry and biotechnology》1991,27(2):163-171
Immobilization of glucoamylase (EC 3.2.1.3) on Celite R649 bio-catalyst carrier for hydrolysis of maltose and maltodextrin has been investigated in both packed bed and recirculated batch reactors. The kinetics parameters on the hydrolysis of maltose were estimated from the packed bed reactor. It is found that this immobilized enzyme is as efficient as the soluble enzyme in catalyzing hydrolysis of maltose. However, it is less efficient than the soluble enzyme in hydrolyzing 30% (w/v) maltodextrin, giving a maximum dextrose equivalent (DE) value of 96.0% instead of 98.2%. 相似文献
6.
A new dioxime ligand, (2E,3E)-3-[(6-{[(1E,2E)-2-(hydroxyimino)-1-methylpropylidene]amino}-pyridin-2-yl)imino]butan-2-one oxime, (H2Pymdo) (3) has been synthesized in H2O by reacting 2,3-butenedione monoxime (2) with 2,6-diaminopyridine. Mono-, di- and tri-nuclear copper(II) complexes of the dioxime ligand (H2Pymdo) and/or 1,10-phenanthroline have been prepared. The dioxime ligand (H2Pymdo) and its copper(II) complexes were characterized by 1H-n.m.r., 13C-n.m.r. and elemental analyses, magnetic moments, i.r. and mass spectral studies. The mononuclear copper(II) complex of H2Pymdo was found to have a 1:1 metal:ligand ratio. Elemental analyses, stoichiometric and spectroscopic data of the metal complexes
indicated that the metal ions are coordinated to the oxime and imine nitrogen atoms (C=N). In the dinuclear complexes, in
which the first Cu(II) ion was complexed with nitrogen atoms of the oxime and imine groups, the second Cu(II) ion is ligated
with dianionic oxygen atoms of the oxime groups and are linked to the 1,10-phenanthroline nitrogen atoms. The trinuclear copper(II)
complex (6) was formed by coordination of the third Cu(II) ion with dianionic oxygen atoms of each of two molecules of the mononuclear
copper(II) complexes. The data support the proposed structure of H2Pymdo and its Cu(II) complexes. 相似文献
7.
Serdar Öğüt Juan C. Idrobo Julius Jellinek Jinlan Wang 《Journal of Cluster Science》2006,17(4):609-626
We examine low-energy isomeric forms, static polarizabilities, and optical absorption spectra of Ag
n
, n = 2–8, and Au
n
, n = 2–3, clusters using first principles computations within the static and time-dependent versions of the density functional theory. The noticeable decrease in the static polarizabilities of Ag7 and Ag8 compared to the values characteristic of Ag
n
, n = 2–6, is correlated with the transition from two-dimensional to three-dimensional structures at n = 7. The optical spectra computed within the time-dependent local density approximation for the most stable structures are in good agreement with the available experimental data and the results of earlier theoretical studies. Optical spectra of higher-energy isomers typically present features that are not observed in the experimental spectra. The d electrons affect the spectra of noble metal clusters by quenching the oscillator strengths through screening of the s electrons and by getting directly involved in the excitations. Due to the larger s–d hybridization in Au compared to Ag, these effects are more pronounced in Au
n
clusters. 相似文献
8.
A new binucleating macrocycle incorporating four exocyclic oxime groups, 6,6′-methylene-bis[1,12–di(hydroximino)-2,3;9,10–dibenzo-1,11–diaza-4,8–dithiacyclotridecane]
(LH4) has been synthesized, its mononuclear CoIII and hetropolynuclear CoIII-PdII complexes have been prepared. LH4 and its
metal complexes have been characterized by elemental analysis, 1H- and 13C-n.m.r., i.r. and mass spectral studies. The elemental
analysis, stoichiometry and the spectroscopic data of the mononuclear CoIII complex indicate that the CoIII ions are coordinated
by the oxime nitrogen atoms (C=N); PdII ions in the latter complex are coordinated through diaza-dithia moiety on the macrocycle.
The mononuclear CoIII complex of LH4 has a 1:1 metal:ligand ratio. All spectral data support the proposed structure of LH4
and its complexes.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
9.
Polymeric copper(II) and nickel(II) complexes of a binucleating tetraoxime macrocycle, 6,6-methylene-bis[1,12-di(hydroximino)- 2,3;9,10-dibenzo-1,11-diaza-4,8-dithiacyclotridecane] (H4L), have been prepared and characterised by elemental analysis, magnetic moments, i.r., uv/vis., and e.p.r. spectral studies. I.r. spectra show that the ligand acts in a tetradentate manner and coordinates via N, S and O donor atoms. The geometry of the resulting metal chelates is discussed with the help of magnetic and spectroscopic measurements. The elemental analyses, stoichiometry and the spectroscopic data of the complexes indicate that the copper(II) and nickel(II) ions are coordinated by the coordination environment of the ligand. The spectral data suggest a distorted tetragonal geometry for polymeric copper(II), and nickel(II) ions in the complexes. The stoichiometry of the metal-to- H4L ratio of complexes (2) and (3), prepared from CuCl2 and NiCl2 respectively, was 3:1, suggesting the formation of polymeric species. 相似文献
10.