$CH_3$OH용매에서 란탄족 원소{Ln(III)=Pr, Sm, Gd, Dy}-거대고리 착물과 한자리 리간드 간의 화학평형(제1보)

Chemical Equilibria of Lanthanides{Ln(III)=Pr, Sm, Gd, Dy}-Macrocyclic Complexes with Monodentate Ligands in $CH_3$OH(Part I)

  • 변종철 (Department of Chemistry, Cheju National University) ;
  • 박유철 (Department of Chemistry, Kyungpook National University) ;
  • 박신복 (Department of Chemistry, Cheju National University)
  • 발행 : 19990600

초록

2,6-diformyl-p-creso1(DFPC)로부터 합성한 Ln-거대고리([20]DOTA) 착물, [Ln([20]DOTA)(NO3)(H2O)](NO3)2 xH2O{Ln(III)=Pr, Sm, Gd, Dy}를methanol용매에 2일정도 정치함으로써 [Ln([20]DOTA)(NO3)(CH3OH)]2+을 얻을 수 있다. 이 lanthanide-거대고리 착물에서 배위 된 CH3OH이 주게원자가 N인 보조리간드,La(=한자리 리간드;pyidine, imidazole, triethylamine, diethylamine, piperidine)에 의해 치환될 때 평형상수(K)를 25 oC, ㅒ=0.1M에서 분광학적 방법으로 결정하였다. 보조리간드의 pKa는 pyridine

Ln-macrocyclic([20]DOTA) complexes, [Ln([20]DPTA)(NO_{3})(H_{2}O)](NO_{3})_{2} \cdotxH_{2}O{Ln(III)=Pr, Sm, Gd, Dy}, which had been synthesized from 2, 6-diformyl-p-cresol(DFPC), was placed in methanol for 2 days, and $[Ln([20]DPTA)(NO_{3})(CH_{3}OH)]^{2+}$ was formed. The equilibrium constants(L) for the substitution of coordinated $CH_{3}OH$ in the Ln-[20]DOTA complexes by various auxiliary ligands, $L_{a}(=monodentate ligands; pyridine, imidazole, triethylamine, diethylamine, piperidine) were determined spectroscopically at $25^{\circ}C$ and 0.1M. The pKa of auxiliary ligand is in the order of pyridine < imidazole < triethylamine < diethylamine < piperidine, however the K has shown the trend of pyridine < imidzole < diethylamine < piperidine < triethylamine.

키워드

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