Synthesis and Reactivity of Copper(II) Complexes with New Binucleating Ligands Derived from 16-or 20-Membered N4-Macrocycles

1990 ◽  
Vol 45 (1) ◽  
pp. 39-44 ◽  
Author(s):  
Yuzo Nishida

Abstract New binucleating ligands, (L1) N ,N′,N″,N‴-tetrakis(2-benzimidazolylmethyl)-1,4,9,12-tetra-azacyclohexadecane, and (L2) N ,N′,N″,N‴-tetrakis(2-benzimidazolylmethyl)-1,4,11,14-tetra-azacycloeicosane were prepared. From the reaction mixture of copper(II) salt and the ligand, new binuclear copper(II) complexes, Cu2(L1) (NO3)4 (1), Cu2(L2)(NO3)4 (2), Cu2(L2)Br4 (3), and trinuclear complexes, Cu3(L1)Cl6 (4), and Cu3(L2)Cl6 (5) were obtained. Cyclic voltammograms revealed that the trinuclear complexes 4 and 5 are composed with the binuclear complex (1 or 2) and [CuCl4]2-. The interaction between two metal ions in the binuclear complexes are confirmed on the basis of the ESR spectra. These binuclear complexes exhibit higher catalytic activity for the oxidation of TMPD by O2 molecule than those of structurally rigid binuclear copper(II) complexes and of flexible binuclear complexes in which two copper(II) coordination sites are linked by a single polyatomic chain.

1992 ◽  
Vol 47 (1) ◽  
pp. 109-114 ◽  
Author(s):  
Yuzo Nishida ◽  
Izumi Watanabe ◽  
Kei Unoura

The cyclic voltammograms of some binuclear copper(II) compounds with binucleating ligands where two molecules of tridentate ligand, N, N -bis(benzimidazol-2-ylmethyl)amine are linked by several alkyl chains, were measured under both argon and dioxygen. The results demonstrate that the binuclear copper(I) species produced by electrochemical reduction exhibit high reactivity towards dioxygen, while the reaction of the corresponding mononuclear species with oxygen is very slow. Thin-layer coulometry ([binuclear copper(I)]/[O2] = 0.47 - 10.6) and thin-layer cyclic voltammetry ([binuclear copper(I)]/[O2] = 4.3 - 10.6 ) revealed that two molecules of the binuclear copper(I) species react with one molecule of dioxygen.


2014 ◽  
Vol 2014 ◽  
pp. 1-9
Author(s):  
K. Jothivenkatachalam ◽  
S. Chandra Mohan

New symmetrical binucleating ligands N,N-bis[2-hydroxy-5-methyl-3-(4-methyl-piperazinomethyl)benzyl]-alkylamines L1 and L2 and their copper(II) complexes [Cu2L(X)2]·2H2O, where X = CH3COO−, C6H5COO−, Cl−, and ClO4-, were prepared and characterised. All the complexes undergo quasi-reversible reduction at negative potential (E = −0.48 to −1.02 V). The acetate and benzoate complexes undergo a two-step single electron transfer at –0.48 to –0.60 V and −0.9 to −1.02 V. The chloro and perchlorate complexes undergo a single step two-electron transfer at −0.55 to −0.75 V. Variable temperature magnetic studies show the presence of weak exchange interaction for acetate (−2 J around 25 to 40 cm−1) and benzoate (−2 J around 45 to 55 cm−1) bridged complexes and no exchange interaction is found for chloro and perchlorate complexes. ESR spectra of chloro and perchlorate complexes are like mononuclear copper(II) complexes with hyperfine splitting (A = 165 ± 5, g∥ = 2.17–2.23, and g⊥ = 2.05–2.10). The ESR spectra of acetate and benzoate complexes are like binuclear copper(II) complexes with broad signal (g = 2.2).


1983 ◽  
Vol 61 (1) ◽  
pp. 57-62 ◽  
Author(s):  
Graham Bullock ◽  
Frederick W. Hartstock ◽  
Laurence K. Thompson

Mononuclear and binuclear copper(II) complexes of the potentially tetradentate binucleating ligands 1,4-di(3′-methyl-2′-pyridyl)aminophthalazine (PAP3Me) and 1,4-di(5′-methyl-2′-pyridyl)aminophthalazine (PAP5Me) are reported. In the case of the ligand 1,4-di(4′,6′-dimethyl-2′-pyridyl)aminophthalazine (PAP46DiMe) only binuclear derivatives were obtained. The mononuclear complexes, involving protonated ligand, result from the sensitivity of these ligands to mildly acidic conditions in aqueous solutions of certain copper salts. Binuclear, neutral ligand, complexes are also formed when the pH increases. Hydroxy bridged binuclear structures exist in all the binuclear complexes described with the exception of one acetate bridged derivative. Sub normal magnetic moments are observed for all the binuclear complexes (< 1.74 BM) indicating spin coupled systems with very low values (< 0.88 BM) for binuclear complexes of PAP46DiMe, indicating the possibility of strong antiferromagnetic exchange between the metal centres.


1981 ◽  
Vol 46 (10) ◽  
pp. 2354-2363 ◽  
Author(s):  
Svatomír Kmošták ◽  
Karel Setínek

The catalytic activity of sulphonated macroporous styrene-divinylbenzene copolymers, the exchange capacity of which was neutralized from 30, 50 and 80% by Fe(III) ions and from 30% by Na ions and that of Wofatit Y-37 ion exchanger neutralized from 10% of its total exchange capacity by several transition metal ions and by sodium has been studied in isomerisation of cyclohexene and dehydration of 1-propanol in the gas phase at 130 °C. It was demonstrated that in both reactions transition metal ions exhibit additional effect to the expected neutralization of the polymer acid groups. In the case of cyclohexene isomerization, this effect depends on the degree of crosslinking of polymer mass of the catalyst. Such dependence has not been, however, observed in dehydration of 1-propanol. The type of transition metal ions did not exhibit any significant effect on the catalytic activity of the polymer catalysts studied.


2021 ◽  
Vol 19 (1) ◽  
pp. 772-784
Author(s):  
Moamen S. Refat ◽  
Ahmed Gaber ◽  
Walaa F. Alsanie ◽  
Mohamed I. Kobeasy ◽  
Rozan Zakaria ◽  
...  

Abstract This article aimed at the synthesis and molecular docking assessment of new diimine Schiff base ligand, namely 2-((E)-(2-((Z)-2-(4-chlorophenyl)-2-hydroxyvinyl)hydrazono) methyl)-6-methoxyphenol (methoxy-diim), via the condensation of 1-(4-chloro-phenyl)-2-hydrazino-ethenol compound with 2-((E)-(2-((Z)-2-(4-chlorophenyl)-2-hydroxy vinyl) hydrazono)methyl)-6-methoxyphenol in acetic acid as well as the preparation of new binuclear complexes of Co(ii), Ni(ii), Cu(ii), and Zn(ii). The following synthesized complexes were prepared in a ratio of 2:1 (metal/ligand). The 1H-NMR, UV-Vis, and FTIR spectroscopic data; molar conductivity measurements; and microanalytical, XRD, TGA/DTG, and biological studies were carried out to determine the molecular structure of these complexes. According to the spectroscopic analysis, the two central metal ions were coordinated with the diamine ligand via the nitrogen of the hydrazine and oxygen of the hydroxyl groups for the first metal ions and via the nitrogen of the hydrazine and oxygen of the phenol group for the second metal ions. Molecular docking for the free ligand was carried out against the breast cancer 3hb5-oxidoreductase and the 4o1v-protein binding kidney cancer and COVID-19 protease, and good results were obtained.


Separations ◽  
2021 ◽  
Vol 8 (11) ◽  
pp. 211
Author(s):  
Keisuke Ohto ◽  
Nako Fuchiwaki ◽  
Hiroaki Furugou ◽  
Shintaro Morisada ◽  
Hidetaka Kawakita ◽  
...  

We prepared acetic acid derivatives using three different frameworks, calix[4]arene, alkenyltrimethylol, and trihydroxytriphenylmethane, which differ in the number and size of their coordination sites. We further investigated the extraction properties for aluminum group metal ions. All three extraction reagents exhibited increased extraction compared with the corresponding monomeric compounds, owing to structural effects. The extraction reaction and extraction equilibrium constants were determined using a slope analysis. Their extraction abilities, separation efficiencies, and potential coordination modes are discussed using the extraction equilibrium constants, half-pH values, and spectroscopic data. The calix[4]arene and trihydroxytriphenylmethane derivatives demonstrated allosteric co-extraction of indium ions (In3+) with an unexpected stoichiometry of 1:2.


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