• Journal of the Korean Chemical Society
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• v.36 no.5
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• pp.709-719
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• 1992

We synthesized the binuclear tetradentate Schiff base cobalt(II), nickel(II) and copper(II) complexes such as [Co(II)_2(TSBP)(L)_4], [Ni(II)_2(TSBP)(II)_4] and [Cu(II)_2(TSBP)] (TSBP: 3,3',4,4'-tetra(salicylideneimino)-1,1'-biphenyl, L: Py, DMSO and DMF). We identified the binucleated structure of these complexes by elemental analysis, IR-spectrum, UV-visible spectrum, T.G.A. and D.S.C. According to the results for cyclic voltammogram and differential pulse polarogram of 1 mM complexes in nonaqueous solvents included 0.1M TEAP-L (L; Py, DMSO and DMF) as supporting electrolyte, it was found that diffusionally controlled redox processes of four steps through with one electron for binucleated Schiff base Cobalt(II) complex was Co(III)_2 {^\longrightarrow \\_\longleftarrow^e^-}Co(III)Co(II)_2{^\longrightarrow \\_\longleftarrow^e^-}Co(II){^\longrightarrow \\_\longleftarrow^e^-}Co(I){^\longrightarrow \\_\longleftarrow^e^-}Co(I)_2 and two steps with one electron for Nickel(II) and Copper(II) complexes were M(II)_2 {^\longrightarrow \\_\longleftarrow^e^-}M(I)M(I){^\longrightarrow \\_\longleftarrow^e^-}M(I)_2 (M; Ni and Cu) in nonaqueous solvents.

• Analytical Science and Technology
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• v.8 no.1
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• pp.55-62
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• 1995

Tetradentate Schiff base cobalt(II) complexes such as $Co(II)_2-N$, N-bis(salicylidene)-m-phenylendiimine; [$Co(II)_2(SMPD)_2(H_2O)_4$] and $Co(II)_2-N$, N-bis(salicylidene)-p-phenylendiimine: [$Co(II)_2(SPPD)_2(H_2O)_4$], and oxygen adducted cobalt (III) complexes such as [$Co(III)_2O_2(SMPD)_2(Py)_2$] and [$Co(III)_2O_2(SPPD)_2(Py)_2$] in pyridine solutions were synthesized. It was identified that the oxygen adducted cobalt(III) complexes have hexacoordinated octahedral configuration with pyridine and oxygen from the measurement of elemental analysis, AA, IR spectra, and TGA. The redox processes were investigated for the oxygen adducted complexes in 0.1M TEAP-pyridine solution, using cyclic voltammetry on the glassy carbon electrode. The redox processes of oxygen adducted Co(III) complexes result in $$[Co(III)_2-O_2-CO(III)]\rightarrow^{e^-}[Co(III)-O_2-Co(II)]\rightarrow^{e^-}[Co(II)-O_2-Co(II)]\rightleftarrows^{e^-}[Co(II)+Co(II)+O_2{\cdot}^-]\rightleftarrows^{e^-}[Co(II)+Co(I)+O_2{\cdot}^-]\rightleftarrows^{e^-}[Co(I)+Co(I)+O_2{\cdot}^-]$$.

• Journal of the Korean Chemical Society
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• v.63 no.1
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• pp.29-36
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• 2019

A potentially tetradentate Schiff base ligand, 2-((2-((pyridin-2-ylmethylene)amino)ethyl)amino)ethan-1-ol (PMAE), and its cadmium(II) complex, [$Cd(PMAE)I_2$] (1), were prepared and characterized by elemental analysis, FT-IR, Raman, $^1H$ and $^{13}C$ NMR spectroscopies and single-crystal X-ray diffraction. In the crystal structure of 1, the cadmium atom has a slightly distorted square-pyramidal geometry and a $CdN_3I_2$ environment in which the PMAE acts as an $N_3$-donor. In the crystal packing of the complex, the alcohol and amine groups of the coordinated ligands participate in hydrogen bonding with iodide ions and form $R^2{_2}(14)$ and $R^2{_2}(8)$ hydrogen bond motifs, respectively. In addition to the hydrogen bonds, the crystal network is stabilized by ${\pi}-{\pi}$ stacking interactions between pyridine rings. The thermodynamic stability of the isolated ligand and its cadmium complex along with their charge distribution patterns were studied by DFT and NBO analysis.

• Journal of the Korean Chemical Society
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• v.36 no.6
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• pp.894-905
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• 1992

Dioxygen binding and homogeneous catalytic oxidation of hydrazobenzene were investigated by employing tetradentate Schiff base Cobalt(II) complexes such as Co(II)(SED)$(Py)_2$, Co(II)(SOPD)$(Py)_2$ and Co(II)(SND)$(Py)_2$ in saturated oxygen methanol solvent. The major product of hydrazobenzene ($H_2$AB) oxidation by catalysts of superoxo type [Co(III)(SED)(Py)$O_2$] and [Co(III)(SOPD)(Py)$O_2$] complexes are trans-azobenzene (t-AB) and rate constants k for oxidation reaction was 7.692 ${\times}$ $10^{-2}$ M/sec for [Co(III)(SED)(Py)$O_2$] and 5.076 ${\times}$ $10^{-2}$ M/sec for [Co(III)(SOPD)(Py)$O_2$]. But cis-azobenzene (c-AB) are obtained as a major product with ${\mu}$-peroxo type [Co(III)(SED)(Py)]$_2O_2$ catalyst, and rate constant k is 1.266 ${\times}$ $10^{-2}$ M/sec. The rate constants of oxidation reaction has been studied spectrophotometrically and the rate law established. A mechanism involving a intermediate activated complexes of catalyst, hydrazobenzene and oxygen has been proposed. $H_2$AB + Co(II)(Schiff base)$(Py)_2$ + $O_2$ ${\rightleftharpoons}_{MeOH}^K$ Co(III)(Schiff base)(Py)$O_2$${\cdot}$$H_2$AB + Py $\longrightarrow^k$ Co(II)(Schiff base)$(Py)_2$ + t-AB + $H_2O_2$(Scchiff base : SED and SOPD). $H_2$AB + 2Co(II)(SND)$(Py)_2$ + $O_2$ ${\rightleftharpoons}_{MeOH}^K$ [Co(III)(SND)(Py)]$_2O_2$${\cdot}$H_2$AB + 2Py ${\longrightarrow}^k$ (Co(II)(SND)$(Py)_2$ + c-AB + $H_2O_2$.

• Journal of the Korean Chemical Society
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• v.55 no.3
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• pp.436-443
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• 2011

The solid complexes of La(III), Ce(III), Pr(III), Nd(III), Sm(III) and Gd(III) with 4-hydroxy-3-(1-{2-(2,4-dihydroxy-benzylidene)-amino phenylimino}-ethyl)-6-methyl-pyran-2-one ($H_2$L) derived from o-phenylenediamine, 3-acetyl-6-methyl-(2H)pyran,2,4(3H)-dione (dehydroacetic acid or DHA) and 2, 4-dihydroxy benzaldehyde have been synthesized and characterized by elemental analysis, conductometry, magnetic susceptibility, UV-visible, FT-IR, $^1H$-NMR, X-ray diffraction, thermal analysis study, and screened for antimicrobial activity. The FT-IR spectral data suggest that the ligand behaves as a dibasic tetradentate ligand with ONNO donor atoms sequence towards central metal ion. From the microanalytical data, the stoichiometry of the complexes has been found to be 1:1 (metal: ligand). The physico-chemical data suggests distorted octahedral geometry for La(III), Ce(III), Pr(III), Nd(III), Sm(III) and Gd(III) complexes. The X-ray diffraction data suggests monoclinic crystal system for La(III) and Ce(III) and orthorombic crystal system for Pr(III) and Nd(III) complexes. Thermal behavior (TG/DTA) of the complexes was studied and kinetic parameters were determined by Horowitz-Metzger and Coats-Redfern methods. The ligand and its metal complexes were screened for antibacterial activity against Staphylococcus aureus, Escherichia coli, Bacillus Sp. and fungicidal activity against Aspergillus Niger, Trichoderma and Fusarium oxysporum.

• Journal of the Korean Chemical Society
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• v.35 no.4
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• pp.379-388
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• 1991

We synthesized the binuclear Tetradentate Schiff base cobalt (II) complexes; [Co(II)$_2$(SMPD)$_2$(L)$_2$] and [Co(II)$_2$(SPPD)$_2$(L)$_2$] (where, SMPD: N,N'-bis(salicylaldehyde)-m-phenylenediimine, SPPD: N,N'-bis(salicylaldehyde)-p-phenylenediimine, L: Py, DMSO and DMF). We identified the binuclear structure of these complexes by elemental analysis, IR-spectrum, and T. G. A. According to the results of cyclic voltammetry and DPP measurements in aprotic solvents containing 0.1M TEAP as supporting electrolyte, it was found that diffusionally controlled redox process of two step for one electron was reversible or quasi reversible process in 0.1M TEAP-pyridine and 0.1M TEAP-DMSO solution at mononuclear complexes; [Co(II)(SOPD)(L)$_2$]. But, we knew that diffusionally controlled reduction processes of four steps with one electron for binuclear [Co(II)$_2$(SMPD)$_2$(L)$_2$] and [Co(II)$_2$(SPPD)$_2$(L)$_2$] complexes was Co(III)$_2\;{\longrightarrow^e}$ Co(III)Co(II) ${\longrightarrow^e}$ Co(II)$_2\;{\longrightarrow^e}$ Co(II)Co(I) ${\longrightarrow^e}$ Co(I)$_2$ in aprotic solvents.

• Journal of the Korean Chemical Society
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• v.35 no.1
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• pp.24-37
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• 1991

We synthesized the binuclear Tetradentate Schiff base nickel(II) and copper(II) complexes ; [Ni(II)$_2$(SMPO)$_2$(L)$_2$], [Ni(II)$_2$(SPPD)$_2$(L)$_2$] and [Cu(II)$_2$(SMPD)$_2$] and [Cu(II)$_2$(SPPD)$_2$] (where, L : Py, DMSO and DMF). We identified the structure of these complexes by elemental analysis, IR-spectrum, T.G.A, D.S.C and ESR measurements. According to the results of cyclic voltammetry and DPP measurements in aprotic solvent included 0.1M TEAP as supporting electrolyte, we knew that diffusional controlled redox process of one step with one electron was irreversible process in 0.1M TEAP-Py solution. Also it was reversible or quasi reversible process in 0.1M TEAP-DMSO solution and reversible or E.C reaction mechanism in 0.1M TEAP-DMF solution at mononuclear complexes ; [Cu(II)(SOPD)] and [Ni(II)(SOPD)(L)$_2$]. But, we knew that diffusional controlled redox process of two step for one electron of binuclear complexes was as follows. The values of redox potential for dimeric complexes in 0.1M TEAP-L solution (where, L ; Py, DMSO and DMF) with scan rate 100mV/sec.

• Bulletin of the Korean Chemical Society
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• v.29 no.1
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• pp.94-98
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• 2008

A fundamental study was developed concerning the novel solvent extraction of the tetravalent metal ions; zirconium(IV), hafnium(IV) and thorium(IV). Their extraction behavior in toluene was investigated with a recently synthesized naphthol-derivative Schiff base, 1-({[4-(4-{[(E)-1-(2-hydroxy-1-naphthyl)methyliden]amino}phenoxy) phenyl]imino}methyl)-2-naphthol (HAPMN). The spectrophotometrical examination of the complex formation between HAPMN and the Zr(IV), Hf(IV) and Th(IV) ions in acetonitrile revealed the formation of stable 1:1 complexes in the solution. After the thorium extraction in toluene, it was found that [Th(OH)3HA] was the respective deriving substance. While, in the case of zirconium and hafnium extraction, the extracted adduct was found to be [M4(OH)8(H2O)16Cl62HA]. The stoichiometric coefficients of these extracted species were determined by the slope analysis method. The extraction reaction followed a cation exchange mechanism.

• Journal of the Korean Chemical Society
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• v.36 no.2
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• pp.261-272
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• 1992

Tetradentate Schiff base Cobalt(II)(3MeOSED)$(H_2O)_2$ complexe was synthesized and allowed to react with dry oxygen to form oxygen adducts of Cobalt(III) complexes such as ${\mu}$-peroxo type [Co(III)(3MeOSED)(DMF)]$_2O_2$ and [Co(III)(3MeOSED)(DMSO)]$_2O_2$in DMF and DMSO or superoxo type [Co(III)(3MeOSED)(Py)]$O_2$ in pyridine. The oxygen adducted complex was investigated by cyclic voltammetry and DPP method with glassy carbon electrode in 0.1M TEAP-DMF (-DMSO,-Py) as supporting electrolyte solution. As a result the reduction reaction process occurred to four steps including prewave Of $O_2^-$in 1 : 1 oxygen adducted superoxo type [Co(III)(3MeOSED)(Py)]$O_2$complex and three steps not including prewave of $O_2^-$ in 1 : 2 oxygen adducted ${\mu}$-peroxo type [Co(III)-(3MeOSED)(DMF)]$_2O_2$ and [Co(III)(3MeOSED)(DMSO)]$_2O_2$. A superoxo type [Co(III)(3MeOSED)(L)]$O_2\;(L: CH_3OH)$ was generated with oxygen in methanol. Selectively oxidized hydrazobenzene $(H_2AB)$ to trans-azobenzene(t-AB) and the rate constant k for oxidation reaction of the following equation is $(2.96 {\pm} 0.2)$${\times}$ $10^{-1}$M/sec. $H_2AB$ + Co (II)(3MeOSED)$(L_2)+O_2\;{\rightleftarrow^K}$ [Co(III)(3MeOSED)(L)]$O_2{\cdot}H_2AB{\longrightarrow^K}$ Co(II(3MeOSED)$(L)_2$+t-AB+$H_2O_2 $.

• Journal of the Korean Magnetic Resonance Society
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• v.18 no.2
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• pp.74-81
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• 2014

The $N_2O_2$ tetradentate Schiff base ligand, N,N'-bis(salicylidene)pentane-1,3-diamine (Salpn), coupled with 1:2 concentration ratio of 1,3-diaminopentane and salicylaldehyde was used to produce a series of macrocyclic Nikel(II) complexes. In the metal complexation, it was observed that Salpn macrocyclic ligand can adopt more than a metal ion giving an unique multinuclear metal complexes including Ni(II)Salpn and $Ni(II)_3(Salpn)_2$. Characteristic IR ${\upsilon}(M-O)$ peaks for Ni(II)Salpn and $Ni(II)_3(Salpn)_2$ were observed to be $1028cm^{-1}$ and $1024cm^{-1}$, respectively. Characteristic UV-Vis absorption ${\lambda}_{max}$ peaks for $Ni(II)_3(Salpn)_2$ were observed to be 241nm and 401 nm. Structural characterization of $Ni(II)_3(Salpn)_2$ by NMR exhibits that the salicylidene ring moiety has two different resonance signals originated from the magnetically asymmetric diligand and trinuclear bis complex. Complete NMR signal assignments and characterizations elucidating structural features of $Ni(II)_3(Salpn)_2$ were described in detail.