• Journal of the Korean Chemical Society
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• v.35 no.2
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• pp.119-127
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• 1991

The protonation and the metal ion complexation of 15 to 18 membered diaza crown ether such as 1,12-diaza-3, 4 : 9, 10-dibenzo-5, 8-dioxacyclopentadecane(NtnOenH$_4$), 1,13-diaza-3,4 : 10,11-dibenzo-hydroxy-5,9-dioxacyclohexadecane(NtnOtnH$_4$), 1,13-diaza-3,4 : 10,11-dibenzo-15-hydroxy-5,9-dioxacyclohexadecane(Ntn(OH)OtnH$_4$), 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacycloheptadecane (NenOdienH$_4$) and 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacyclooctadecane(NtnOdienH$_4$) were studlied by potentiometry and NMR spectroscopy. The protonation constants were used to predict basicity of crown ethers. The sequence of the basicity was NenOdienH$_4$ < Ntn(OH)OtnH$_4$ < NtnOenH$_4$ < NtnOtnH$_4$ < NtnOdienH$_4$. Changes on the basicity were explained in terms of the effects of substituents and the degree of twistness of the macrocyclic ring. The sequence of the complex stabilities were Co(II) < Ni(II) < Cu(II) < Zn(II) for the transition metal complexes and Cd(II) < pb(II) < Hg(II) for the post-transition metal complexes. These changes on the stabilities were dependent on the basicity of the ligand and cavity size of the ring. For the heavy post-transiton metal complexes and Zn(Ⅱ) complex, the former factor was predominent and for the other transition metal complexes, the latter was affected on the stabilities. $^1$H and $^{13}$C-NMR studies for heavy post-transition metal complexes indicated that the nitrogen atom has greater affinity on metal ions than oxygen atom and the planarity of the rings was losed by the complexation with metal ions.

• Journal of the Korean Chemical Society
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• v.43 no.6
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• pp.628-635
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• 1999

Direct preparative method of 2,6-diformyl-p-cresol and 2-hydroxy-3-hydroxy-5-methylbenzaldehyde from 2,6-bis(hydroxymethyl)-4-methylphenol using activated $Mn(IV)O_2$ was described. Hexadentate compartmental Iigands, $H_4L[A]\;and\; H_4L[B]$ were prepared by condensation reactions of 2-hydroxy-3-hydroxy methyl-5-methylbenzaldehyde with ethylenediamine and 1,3-diaminopropane respectively. By the reaction of macrocycle($H_4[20]DOTA$) with Ln(III) nitrate {Ln(III)=Pr, Sm, Cd, Dy }, discrete mononuclear Ln(III) complexes of the type $[Ln(H_2[20]DOTA)(ClO_4)(H_2O)]\;{\cdot}\;3H_2O$ were synthesized in the solid state. $[Ln([20]DOTA)(NO_3)(H_2O)](NO_3)_2\;{\cdot}\;xH_2O$ was placed in methanol for 2 days, and $[Ln([20]DOTA)(NO_3)(CH_3OH)]^{2+}$ was formed. The equilibrium constants(K) for the substitution of coordinated $CH_3OH$ in the Ln-[20]DOTA complexes by various auxiliary ligand, $L_a$(=salicylic acid, p-chlorobenzoic acid, benzoic acid, acetic acid, 4-bromophenol) were determined spectroscopically at 25$^{\circ}C$ and 0.1M $NaClO_4$. The K values calculated were in the order of salicylic acid > p-chlorobenzoic acid > benzoic acid > acetic acid > 4-bromophenol, while pKa of auxiliary ligands was in the opposite trend.

• Journal of the Korean Chemical Society
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• v.48 no.6
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• pp.577-582
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• 2004

The azacrown compounds, 1,4-dioxa-7,10,13-triazacyclopentadecane-N,N',N''-triacetic acid, $N-ac_3[15]aneN_3O_2(II_a)$ and 1,4-dioxa-7,10,13-triazacyclopentadecane-N,N',N''-tripropioc acid, $N-pr_3[15]aneN_3O_2(II_b)$ were synthesized by modified methods. Potentiometry was used to determine the protonation constant of the $N-ac_3[15]aneN_3O_2\;and\;N-pr_3[15]aneN_3O_2$. The stability constants of complexes of the trivalent metal ions of $Ce^{3+},\;Eu^{3+},Gd^{3+},and\;Yb^{3+}$ and divalent metal ions of $Co^{2+},\;Ni^{2+},\;Cu^{2+},\;and\;Zn^{2+}$ with the ligands $N-ac_3[15]aneN_3O_2\;and\;N-pr_3[15]aneN_3O_2$ have been determined at $25{\pm}0.1^{\circ}C$ in 0.1 M $NaClO_4$ solution by potentiometric methods. The metal ion affinities of the two triazamacrocyclic ligands with three pendant acetate or propionate groups are compared to those obtained for the similar ligands, 1,7-dioxa-4,10,13-triazacyclopentadecane-N,N',N''-triacetic acid, and 1,7-dioxa-4,10,13- triazacyclopentadecane-N,N',N''-tripropioc acid. The trends in stability of complexes for different metal ions due to changes in the nitrogen position of the donor atoms of the ligand are discussed.

• Journal of the Korean Chemical Society
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• v.31 no.4
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• pp.334-343
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• 1987

The Chemical reactions between $NiL_m{^{2+}}\{$Ni(rac-1[14]7-diene)^{2+},\;Ni(meso-1[14]7-diene)^{2+},\;Ni(1[14]4-diene)^{2+},\;{\alpha}-Ni(rac-[14]-decane)^{2+},\;{\beta}-Ni(rac-[14]-decane)^{2+},\;and\;Ni(meso-[14]-decane)^{2+}$}\and\ CN^-$ ion were studied by the spectrophotometric method. The equilibrium constants (K_1$) for the 1:1 complex ion, $[NiL_m(CN)]^+\;with\;NiL_m{^{2+}}\;and\;CN^-$ ion were determined in the range of 3 to $25^{\circ}C$. The $K_1\;for\;Ni(rac-1[14]7-diene)^{2+},\;Ni(meso-1[14]7-diene)^{2+},\;Ni(1[14]4-diene)^{2+},\;{\alpha}-Ni(rac-[14]-decane)^{2+},\;{beta}-Ni(rac-[14]-decane)^{2+},\;and\;Ni(meso-[14]-decane)^{2+}\;at\;15^{\circ}C$ was 4.7, 5.3, 6.2, 7.5, 9.4, and 9.8, respectively. The values of $K_1$ decreased with increasing temperature. From the temperature effect on equilibrium constant ($K_1$), thermodynamic parameters $({\Delta}H^{\circ},\;{\Delta}S^{\circ},\;{\Delta}G^{\circ})$ for reaction were evaluated and the reaction of $NiL_m{^{2+}}\;and\;CN^-$ ion was exothermic. $NiL_m{^{2+}\;reacts\;with\;CN^-$ ion to give $Ni(CN)_4{^{2-}}$ ion and macrocyclic ligand $(L_m)$. The kinetics of formation of the $Ni(CN)_4{^{2-}}$ ion of varying the $[CN^-],\;[HCN],\;and\;[OH^-]$ have been investigated at 3∼$25^{\circ}C\;and\;0.5M\;NaClO_4$. Maintaining a constant $[CN^-],\;k_{obs}/[CN^-]^2$ increases linearly with increasing [HCN]. In the presence of large quantities of $[OH^-],\;k_{obs}/[CN^-]^2$ also increases linearly with $[OH^-]$. From the temperature effect on kinetic constant (k_{obs})$, parameter of activation $({\Delta}H^{\neq},\;{\Delta}S^{\neq})$ of reaction of $NiL_m{^{2+}}\;with\;CN^-$ ion were determined. For the $Ni(rac-1[14]7-diene)^{2+},\;Ni(meso-1[14]7-diene)^{2+},\;{\alpha}-Ni(rac-[14]-decane)^{2+},\;{\beta}-Ni(rac-[14]-decane)^{2+},\;and\;Ni(meso-[14]-decane)^{2+}\;series\;{\Delta}H^{\neq}$ gradually decrease as the d-d transition energy, $ν(cm^{-1})$ decrease. And the reaction of the five $NiL_m{^{2+}}\;with\;CN^-$ ion take place by way of equal paths.