• Journal of Environmental Science International
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• v.20 no.6
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• pp.687-700
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• 2011

A new $N_3-O_2$ pentadentate ligand, H-BHPT, was synthesized. Hydrochloric acid salts of Br-BHPT, Cl-BHPT, $CH_3O$-BHPT and $CH_3$-BHPT, having Br-, Cl-, $CH_{3-}$ and $CH_3O-$ substituents at the para position of the phenol hydroxyl group of H-BHPT were synthesized. Hydrochloric acid salts of 3OH-BHPT and 4OH-BHPT, having different position of the phenol hydroxyl group of H-BHPT were also synthesized. The synthesis of each ligand was confirmed by C. H. N. atomic analysis and $^1H$ NMR, $^{13}C$ NMR, UV-visible, and mass spectra. The calculated proton dissociation constants ($log{K_n}^H$) of the phenol hydroxyl group and secondary amine group of the synthesized $N_3-O_2$ ligands showed five steps of the proton dissociations. The order of the overall proton dissociation constants ($log{\beta}_p$) of the ligands was Br-BHPT < Cl-BHPT < H-BHPT < $CH_3O$-BHPT < $CH_3$-BHPT. The order agreed with that of Hammett substituent constants (${\delta}_p$). However, dissociation steps of 3OH-BHPT were four and that of 4OH-BHPT was three. The calculated stability constants ($logK_{ML}$) between the ligands and transition metal ions agreed with the order of $log{\beta}_p$ values of the ligands. The order of the stability constants between the transition metal ions with the synthesized ligands was Co(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II). The order agreed well with that of the Iriving-Williams.

• Journal of Environmental Science International
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• v.13 no.9
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• pp.835-843
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• 2004

N,N-bis(2-salicylaldehyde)dipropylenetriamine(5- Hsaldipn), N,N-bis( 5-bromosalicyl-aldehyde) dipropylenetriamine (5-Brsaldipn), N,N-bis(5-chlorosalicy laldehyde )dipropylene-triamine(5-Clsaldipn), N,N-bis(2-hydroxy- $5-methoxy-benzaldehyde)dipropylenetriamine(5-OCH_3saldipn)$ and N,N-bis (2-hydroxy-5-nitrobenzaldehyde)dipropylenetriamine $(5-NO_2saldipn)$ were synthesized and characterized by elemental analysis, infrared spectrometry, NMR spectrometry and mass spectrometry. Their proton dissociation constants were determined in 70% dioxane/30% water solution by potentiometric. Stability constants of the complexes between these ligands and the metal ions such as Cu(II), Ni(II) and Zn(II) were measured in dimethyl sulfoxide by a polarographic method. Stability constants for the ligands were in the order of $5-OCH_3$ > 5-H > 5-Br > 5-Cl > $5-NO_2$ saldipn. Enthalpy and entropy changes were obtained in negative values.

• Journal of Environmental Science International
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• v.15 no.8
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• pp.799-809
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• 2006

Hydrobromic acid salts of new N, N, O tridentate ligands containing phenol, 2-[(2-Methylamino- ethyl- amino)-methyl]-phenol(H-MMP. 2HBr), 5-Bromo-2-[(2-Methylamino-ethylamino)-methyl]-phenol (Br- MMP. 2HBr), 5-Chloro-2-[(2-Methylamino-ethylamino)-methyl]-phenol(Cl-MMP. 2HBr), 5-Methyl-2-[(2-Methylamino-ethylamino)-methyl]-phenol(Me-MMP. 2HBr), 5-Methoxy-2-I(2-Methylamino-ethylamino)- methyl]-phenol(MeO- MMP. 2HBr) and. 1-[(2-Methylamino-ethylamino)- methyl]-naphthalen-2-ol(Nap- MMP. 2HBr) were synthesized. The synthesized ligands were confirmed by C. H. N. atomic analysis, UV-visible and IR spectroscopies, $^1$H NMR, $^{13}$C NMR and mass analysis. The potentiometry study revealed that the proton dissociation constants(logK$_n^H$) of the synthesized ligands and stability constants (logK$_{ML}$, logK$_{LM2}$) of transition metal complexes of Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) ions occurred in three steps and the order of the calculated overall proton dissociation constants(log$\beta_p$) and stability constants (logK$_{ML}$) of ligands was Br-MMP. 2HBr < Cl-MMP 2HBr < H-MMP. 2HBr < Nap-MMP. 2HBr < Me-MMP. 2HBr < MeO-MMP. 2HBr. The order showed a similar trend to that of Hammett substituent constants($\delta_p$). The synthesized ligands usually form 2:1(ML$_2$) complexes with transition metal ions. The order of the stability constants of each transition metal ions was Co(II) < Ni(II) < Cu(II) ;> Zn(II) ;> Cd(II) ;> Pb(II).

• Journal of Environmental Science International
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• v.18 no.7
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• pp.735-746
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• 2009

Hydrochloric acid salt of a new $N_2O_3$ pentadentate ligand, N,N'-Bis(2-Hydroxybenzyl)-1,3-diamino-2-propanol(H-BHDP 2HCl) was synthesized. Br-BHDP 2HCl, CI-BHDP 2HCl, $CH_3-BHDP$ 2HCl and $CH_3O$-BHDP 2HCl having Br, Cl, $CH_3$ and $CH_3O$ substituents at 5-position of the phenol group of H-BHDP 2HCl were also synthesized. The potentiometry study in aqueous solution revealed that the proton dissociations of the synthesized ligands occurred in four steps and their order of the calculated overall proton dissociation constants($log{\beta}_p$) was Br-BHDP < Cl-BHDP < H-BHDP < $CH_3O-BHDP$ < $CH_3-BHDP$. The order showed a similar trend to that of Hammett substituent constants(${\delta}_p$). The order of the stability constants($logK_{ML}$) was Co(II) < Ni(II) < Cu(II) < Zn(II) < Cd(II) < Pb(II). The order in their stability constants ($logK_{ML}$) of each transition metal complex agreed with that of the overall proton dissociation constants ($log{\beta}_p$).

• Journal of Environmental Science International
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• v.21 no.4
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• pp.421-435
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• 2012

Novel $N_2O_2$ tetradentate ligands, H-3BPD and H-2BPD were synthesized. Hydrochloric acid salts of Br-3BPD, Cl-3BPD, Br-2BPD and Cl-2BPD having Br and Cl substituents at the $para$ position of the phenol hydroxyl group, were synthesized. The ligands were characterized by C. H. N atomic analysis, $^1H$ NMR, $^{13}C$ NMR, UV-visible, and mass spectra. The proton dissociation constants ($logK_n{^H}$) of the phenol hydroxyl group and secondary amine of the synthesized $N_2O_2$ ligands were shown by four step wise values. The orders of the calculated overall proton dissociation constants ($log{\beta}_p$) were Br-3BPD < Cl-3BPD < H-3BPD in case of 3BPD and Br-2BPD < Cl-2BPD < H-2BPD in case of 2BPD respectively. The order agreed well with that of $para$ Hammett substituent constants(${\delta}_p$). The stability constants($logK_{ML}$) of the complexes between the synthesized ligands and transition metal(II) ions agreed with the order of $log{\beta}_p$ of the ligands. The order of the $logK_{ML}$ value of the each transition metal (II) ion was Co(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II), which agreed well with that of Iriving-Williams series.

• Journal of Environmental Science International
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• v.19 no.7
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• pp.849-860
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• 2010

A new $N_3O_2$ pentadentate ligand, N,N'-Bis(2-hydroxybenzyl)-ethylenetriamine(H-BHET 3HCl) was synthesized. The hydrochloric acid salts of Br-BHET 3HCl, Cl-BHET 3HCl, $CH_3O$-BHET 3HCl and $CH_3$-BHET 3HCl containing Br-, Cl-, H-, $CH_3O-$ and $CH_3-$ groups at the para-site of the phenol group of the H-BHEP were synthesized. The structures of the ligands were confirmed by C. H. N. atomic analysis and $^1H$ NMR, $^{13}C$ NMR, UV-visible and mass spectra. The calculated stepwise protonation constants(${\logK_n}^H$) of the synthesized $N_3O_2$ ligands showed six steps of the proton dissociation. The orders of the overall protonation constants($\log{\beta}_p$) of the ligands were Br-BHET < Cl-BHET < H-BHET < $CH_3O$-BHET < $CH_3$-BHET. The orders agreed well with that of para Hammett substituent constants(${\delta}_p$). The calculated stability constants($\logK_{ML}$) between the ligands and heavy metal ions (Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II)) agreed well with the order of the overall proton dissociation constants of the ligands but they showed a reverse order in para Hammestt substituent constants(${\delta}_p$). The order of the stability constants between the heavy metal ions with the synthesized ligands were Co(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II).

• Journal of Environmental Science International
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• v.16 no.8
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• pp.913-920
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• 2007

Hydrochloride acid salts of new $N_2O_2$ tetradentate ligands containing amine and phenol N,N'-bis(2-hydroxybenzyl)-o-phenylenediamine(H-BHP), N,N'-bis(5-bromo-2-hydroxybenzyl)-o-phenylenediamine(Br-BHP), N,N'-bis(5-chloro-2-hydroxybenzyl)-o-phenylene-diamine(Cl-BHP), N,N'-bis(5-methyl-2-hydroxybenzyl)-o-phenylene-diamine (Me-BHP) and N,N'-bis(5-methoxy-2-hydroxybenzyl)-o-phenylenediamine(MeO-BHP) were synthesized. The ligands were characterized by elemental analysis, mass and NMR spectroscopy. The elemental analysis showed that the ligands were isolated as dihydrochloride salt. The potentiometry study revealed that the proton dissociation constants$(logK_n{^H})$ of ligands and stability constants $(logK_{ML})$ of transition and heavy metals complexes. The order of the stability constants of each metal ions for ligands was Br-BHP < Cl-BHP > H-BHP < MeO-BHP < Me-BHP.

• Analytical Science and Technology
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• v.19 no.2
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• pp.131-141
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• 2006

Hydrobromic acid salt of a $N_2O_2$ tetradentate ligand, N,N'-bis(2-hydroxybenzyl)-ethylene-diamine ($H-BHE{\cdot}2HBr$) was synthesized. $Br-BHE{\cdot}2HBr$, $Cl-BHE{\cdot}2HBr$, $CH_3-BHE{\cdot}2HBr$ and $CH_3O-BHE{\cdot}2HBr$ having Br, Cl, $CH_3$ and $CH_3O$ substituents at 5-position of the phenol group of $H-BHE{\cdot}2HBr$ were also synthesized. $Nap-BHE{\cdot}2HBr$ having naphthalen-2-ol instead of the phenol group was also synthesized. The potentiometry study in aqueous solution revealed that the proton dissociations of the synthesized ligands occurred in four steps and the order of the calculated overall proton dissociation constants (${\log}{\beta}_p$) of each ligand was Br-BHE < Cl-BHE < H-BHE < Nap-BHE < $CH_3$-BHE < $CH_3O$-BHE. The order showed a similar trend to that of Hammett substituent constants(${\sigma}_P$). The order of the stability constants (${\log}K_{ML}$) was CO(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II). The order in their stability constants (${\log}K_{ML}$) of each transition metal complex agreed well with that of the overall proton dissociation constants (${\log}{\beta}_p$).

• Journal of the Korean Chemical Society
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• v.47 no.6
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• pp.569-577
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• 2003

Ligands, Br-PEMP, Cl-PEMP and $CH_3O-PEMP$ having Br, Cl and $CH_3O$ substituents at 5-position of the $N_2O$ tridentate ligand, 2-[(2-pyridine-2-ethylamio)-methyl]-phenol (H-PEMP) containing pyridine and phenol were synthesized. Another ligand, Naph-PEMP having pyridine and 2-hydroxy-1-naphthalene was also synthesized. The ligands were characterized using elemental analysis, UV-visible, IR, $^1H\;NMR\;and\;^{13}C$ NMR spectroscopy and mass analysis. The potentiometric titration study in aqueous solution revealed that the proton dissociation of the ligands occurred in three steps and the order of overall proton dissociation constants (log${\beta}$) was $CH_3O-PEMP$ > Naph-PEMP > H-PEMP > Cl-PEMP > Br-PEMP. The order of stability constants (logML and log$ML_2$) of their transition metal complexes was Co(II) < Ni(II) < Cu(II) > Zn(II). The order in their stability constants values of each transition metal complex agreed well with that in overall proton dissociation constant value of the ligands.

• Analytical Science and Technology
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• v.9 no.4
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• pp.345-354
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• 1996

Algal(II) Multidentate N, O-Schiff base ligands, such as bis(salicylaldehyde) ethylenediimine(SED), bis(salicylaldehyde) propylenediimine(SPD), bis(salicylaldehyde) diethylenetriimine(SDT), bis (salicylaldehyde) triethylenetetraimine(STT) and bis(salicyl-aldehyde)tetraethylenepentaimine(STP) were prepared. Stepwise proton dissociation constants of the Schiff base were measured potentiometrically in ethanol and a mixture of 70% dioxane and 30% $H_2O$. The stability constants of copper(II)-Schiff base complexes were in the order of Cu(II)-SPD${\leq}$Cu(II)-SED~STT${\leq}$Cu(II)-STP. Oxidation-reduction process of the Cu(II)-Schiff base complexes was involved with one-electron reaction.