ACOMS+ 및 학술지 리포지터리 설명회

  • 한국과학기술정보연구원(KISTI) 서울분원 대회의실(별관 3층)
  • 2024년 07월 03일(수) 13:30
 

  • P-ISSN1225-0163
  • E-ISSN2288-8985
  • SCOPUS, ESCI, KCI

논문 상세

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  • P-ISSN 1225-0163
  • E-ISSN 2288-8985

새로운 산소-질서(N2O2)계 네 자리 리간드의 합성과 전이금속 착물 안정도상수에 대한 치환기 효과

Synthesis of new N2O2 tetradentate ligands and the substituent effect on the stability constants of the transition metal complexes

분석과학 / Analytical Science and Technology, (P)1225-0163; (E)2288-8985
2006, v.19 no.2, pp.131-141
김선덕 (대구대학교)
진경록 (대구대학교)
  • 다운로드 수
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초록

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

keywords
proton disociation constants, potentiometry, stability constants. Corresponding authorPhone : +82-053-850-6444 Fax : +82-053-850-6449E-mail: sdk@deagu.ac.kr132 .......Analytical Science & Technology.... ... -.. (NxOy). .. .. .... ....... ..., ... ., proton disociation constants, potentiometry, stability constants. Corresponding authorPhone : +82-053-850-6444 Fax : +82-053-850-6449E-mail: sdk@deagu.ac.kr132 .......Analytical Science & Technology.... ... -.. (NxOy). .. .. .... ....... ..., ... .

Abstract

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

keywords
proton dissociation constants, potentiometry, stability constants


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