• 한국환경과학회지
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• 제20권6호
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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.

• 한국환경과학회지
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• 제13권9호
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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.

• 한국환경과학회지
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• 제15권8호
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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).

• 한국환경과학회지
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• 제18권7호
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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 ($log{\beta}_p$).

• 한국환경과학회지
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• 제21권4호
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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.

• 한국환경과학회지
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• 제19권7호
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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).

• 한국환경과학회지
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• 제16권8호
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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.

• 분석과학
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• 제19권2호
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• pp.131-141
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• 2006

새로운 산소-질소($N_2O_2$)계 네 자리 리간드 N,N'-bis(2-hydroxybenzyl)-ethylenediamine($H-BHE{\cdot}2HBr$)의 브롬산염을 합성하였다. 또한 $H-BHE{\cdot}2HBr$의 페놀기 5-위치에 치환기로 브롬, 염소, 메틸기 및 메톡시기를 가진 $Br-BHE{\cdot}2HBr$, $Cl-BHE{\cdot}2HBr$, $CH_3-BHE{\cdot}2HBr$ 및 $CH_3O-BHE{\cdot}2HBr$을 합성하였다. 그리고 페놀기 대신에 naphthalen-2-ol을 가진 $Nap-BHE{\cdot}2HBr$도 합성하였다. 합성된 리간드들의 양성자 해리는 수용액에서 전위차 적정한 결과 4 단계로 일어났으며, 계산된 각 리간드의 총괄 양성자 해리상수(${\log}{\beta}_p$) 값은 Br-BHE < Cl-BHE < H-BHE < Nap-BHE < $CH_3$-BHE < $CH_3O$-BHE의 순서로 Hammett 상수(${\sigma}_P$) 값의 순서와 비교적 같은 경향을 나타내었다. 전이금속(II) 이온들의 착물의 안정도상수(${\log}K_{ML}$) 값의 크기는 Co(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II)의 순서이었다. 또한 각 리간드들의 전이금속(II) 이온들의 착물 안정도상수(${\log}K_{ML}$) 값들의 크기 순서도 리간드의 총괄 양성자 해리상수(${\log}{\beta}_p$) 값과 서로 잘 일치하였다.

• 대한화학회지
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• 제47권6호
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• pp.569-577
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• 2003

피리딘과 페놀을 포함하는 N2O계 세 자리 리간드 2-[(2-pyridine-2- ethylamino)-methyl]-phenol(H-PEMP)를 합성하였다. 또한 H-PEMP 페놀의 5-위치에 치환기로 브롬, 염소 및 메톡시를 가지는 Br-PEMP, Cl-PEMP 및 $CH_3O-PEMP$를, 그리고 2-hydroxy-1-naphthalene기를 가진 Naph-PEMP을 합성하였다. 합성된 각 리간드들을 수용액에서 전위차 적정 결과 양성자 해리는 3 단계로 일어났으며, 계산된 각 리간드의 총괄 양성자 해리상수(log${\beta}$) 값은 $CH_3O-PEMP$〉Naph-PEMP〉H-PEMP〉Br-PEMP〉Cl-PEMP의 순서로 Hammett식의 치환기 상수(${\sigma}_p$) 값 크기 순서와 일치하였다. 전이금속 이온들의 착물 안정도상수(logML 및 log$ML_2$) 값의 크기는 금속이온에 따라 Co(II)< Ni(II)< Cu(II)>Zn(II)의 순서이었고, 치환기에 따른 각 리간드의 착물 안정도상수 값은 리간드의 총괄 양성자 해리상수 값의 크기순서와 일치하였다.

• 분석과학
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• 제9권4호
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• pp.345-354
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• 1996

산소-질소를 포함하는 여러 자리 시프염기 리간드인 비스-살리실알데히드-에틸렌디이민(SED), 비스-살리실알데히드-프로필렌디이민(SPD), 비스-살리실알데히드-디에틸렌트리이민(SDT), 비스-살리실알데히드-트리에틸렌테트라이민(STT) 및 비스-살리실알데히드-테트라에틸 렌펜타이민(STP) 등을 합성하고 이들 리간드들을 에탄올과 70% 디옥산 수용액에서 전위차법으로 넷, 다섯 및 여섯 단계의 양성자 해리상수값을 구하였다. 구리(II)-시프염기 착물의 안정도상 수값의 크기는 Cu(II)-SPD${\leq}$Cu(II)-SED~STT${\leq}$Cu(II)-STP 순서로 음전위쪽으로 이동하였다. Cu(II)-시프염기 착물의 산화-환원 과정은 일전자 반응이었다.