대한화학회지 (Journal of the Korean Chemical Society)

  • 제43권6호
  • /
  • Pages.628-635
  • /
  • 1999
  • /
  • 1017-2548(pISSN)
  • /
  • 2234-8530(eISSN)
대한화학회 (Korean Chemical Society)
권호 표지

$CH_3OH$ 용매에서 란탄족 원소{Ln(Ⅲ)=Pr, Sm, Gd, Dy}-거대고리 착물과 보조 리간드 간의 화학평형 (제2보): 주게원자가 산소인 염기를 중심으로 고찰.

Chemical Equilibria of Lanthanides{Ln(Ⅲ)=Pr, Sm, Gd, Dy}-Macrocyclic Complexes with Auxiliary Ligands in $CH_3OH$(PartⅡ):Study of the Coordination of Oxygen-Containing Bases.

  • 변종철 (제주대학교 자연과학대학 화학과) ;
  • 박유철 (경북대학교 자연과학대학 화학과) ;
  • 한충훈 (제주대학교 자연과학대학 화학과)
  • 발행 : 19991200
PDF 다운로드
⟨ 이전 논문 다음 논문 ⟩

초록

활성화된 $Mn(IV)O_2$를 이용하여 2,6-bis(hydroxymethyl)-4-methylphenol로부터 2,6-diformyl-p-cresol과 2-hydroxy-3-hydroxymethyl-5-methylbenzaldehyde를 제조하였다. 2-hydroxy-3-hydroxymethyl-5-methylbenzaldehyde와 ethylenediamine 및 1,3-diaminopropane의 축합반응에 의해 6-배위 칸막이 리간드, $H_4L[A]와\; H_4L[B]$를 각각 얻었다. methanol에서 2,6-diformyl-p-cresol과 1,2-diaminobenzene으로부터 부분적으로 환원된 거대고리, $H_4[20]DOTA$를 얻을 수 있었다. 이 $H_4[20]DOTA$와 lanthanide(IlI) nitrate 간의 반응 또는 methanol에서 주형과정(template procedure)에 의해 일핵 착물, $[Ln(IIl)(H_2[20]DOTA)(ClO_4)(H_2O)]\;{\cdot}\;3H_2O과\; [Ln([20]DOTA)(NO_3)(H_2O)](NO_3)_2\;{\cdot}\;xH_2O$를 각각 합성하였다. $[Ln([20]DOTA)(NO_3)(H_2O)](NO_3)_2\;{\cdot}\;xH_2O$를 2일 정도 methanol에 정치함으로써 얻은 $[Ln([20]DOTA)(NO_3)(CH_3OH)]^{2+}$에서 배위된 $CH_3OH$이 주게원자가 O인 보조리간드, $L_a$(=salicylic acid, p-chlorobenzoic acid, benzoic acid, acetic acid, 4-bromophenol)에 의해 치환될 때 평형상수 (K)를 25$^{\circ}C$, ${\mu}$=0.1M $NaClO_4$에서 분광학적 방법으로 결정하였다. 이 때 평형상수(K) 값들은 보조리간드 pKa 크기의 반대 경향인 salicylic acid>p-chlorobenzoic acid>benzoic acid>acetic acid>4-bromophenol 순서로 나타났다.

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.

키워드

참고문헌

  1. Chem. Soc. Rev. v.18 Randaccio, L;Bresciani-Pahor, N.;Marzilli, L.G.
  2. Acc. Chem. Res. v.26 Battersby, A. R.
  3. J. Am. Chem. Soc. v.115 Zou, X.;Brown, K. L.
  4. Inorg. Chem. v.30 Brown,K.L.;Zou,X.;Salmon,L.
  5. Inorg. Chem. v.34 Zou,X.;Evans,D,R.
  6. Science v.266 Luschinsky-Drennan,C.;Huany,S.;Ludwig,M.L.
  7. Biochemistry v.34 Marsh,E.G.N.
  8. Structure v.4 Ludwig, M.L.;Drennan,C.L.;Matthews,R.G.
  9. J.Am.Chem. Soc. v.115 Waddington,M.;Finke,R.G,
  10. Inorg. Chem. v.35 Garr.C.D.;Sirovatka,J.M.;Finke,R.G.
  11. Inorg. Chem. v.15 Hupp,S.S.;Dahlgren,G.
  12. Inorg. Chem. v.31 Brown,K.L.;Satyanarayana,S.
  13. J.Chem. Soc. Hamza,M.S.A.;Pratt,J.M.
  14. Inorg. Chem. v.34 Victor,A.A.;Silvia, L.;Kadish,K,M.
  15. J. Korean Chem. Soc. v.43 Byun,J. Ch;Park, Y. Ch;Park, Sh.B.
  16. Inorganic Chemica Acta v.202 Aguiari,A.;Bullita, E.;Vigato,P.A.
  17. Inorganica Chemica Acta v.230 Antolovich,M.;Phillips, D.J.;David,Rae,A.
  18. Inorganica Chemica Acta v.256 Aguiari,A.;Tamburini,S.;Vigato, P.A.
  19. Advanced Inorganica Chemistry, ($5^{th}$Ed.) Cotton, F.A.;Wilkinson,G.
  20. Inorg. Chem. v.19 Liang,B.F.;Chung,C.S.