네자리 리간드-황아미노산 금속착물의 산화반응에 의한 배위된 황원자의 sulfoxide 원자단으로의 전환

Conversion of Coordinated Sulfur Atom into Sulfoxide Group via Oxidation Reaction of Metal Complexes of Tetradentates and Sulfur Amino Acids

  • 이숭실 (연세대학교 이과대학 화학과) ;
  • ;
  • 최승락 (연세대학교 이과대학 화학과) ;
  • 전무진 (연세대학교 이과대학 화학과)
  • Sung Sil Lee (Department of Chemistry, Yonsei University) ;
  • Peter Fu (Department of Chemistry, Yonsei University) ;
  • Sung Rack Choi (Department of Chemistry, Yonsei University) ;
  • Moo Jin Jun (Department of Chemistry, Yonsei University)
  • 발행 : 1989.10.20

초록

주게원자가 질소원자와 산소원자인 N2O2형 네자리 리간드 ethylenediamine-N,N'-S-${\alpha}$-isobutylacetic acid(SS-eniba)의 디클로로 로듐(III)$[Rh(SS-eniba)Cl_2]$-의 합성에서 ${\Delta}-s-cis$${\wedge}-uns-cis$ 이성체를 분리하였다. ${\Delta}-s-cis-[Rh(SS-eniba)Cl_2]$- 착물과 S-methyl-L-cystcine(Smc)의 반응으로부터 ${\Delta}-s-cis-[Rh(SS-eniba(Smc)]^+$ 착물을 합성한 다음 $H_2O_2$를 이용한 산화반응으로부터 배위된 황원자가 sulfoxide 원자단으로 산화된 ${\Delta}-s-cis-[Rh(SS-eniba)(Smc-o)]^+(Smc-o=S-methyl-L-cysteine sulfoxide)$ 착물이 형성됨을 관찰하였다. 한편 S-methyl-L-cysteine을 $H_2O_2$와 반응시켜 sulfoxide 원자단으로 산화시킨 S-methyle-L-cysteine sulfoxide의 합성을 별도로 진행한 후 ${\Delta}-s-cis-[Rh(SS-eniba)Cl_2]^+$ 착물에 배위시켜 표준착물인 ${\Delta}-s-cis-[Rh(SS-eniba)(Smc-o)]^+$를 합성한 다음 ${\Delta}-s-cis-[Rh(SS-eniba(Smc)]^+$ 착물을 산화시켜 얻은 ${\Delta}-s-cis-[Rh(SS-eniba)(Smc-o)]^+$착물과 비교하여 배위된 항원자가 sulfoxide 원자단으로 전환되었음을 또한 관찰하였다.

Reaction between the $N_2O_2-type$ tetradentate ligand, ethylenediamine-N,N'-di-S-${\alpha}$-isobutylacetic acid (SS-emiba) and $RhCl_3{\cdot}3H_2O$ has yielded ${\Delta}-s-cis-\;and\;{\wedge}-uns-cis-[Rh(SS-eniba)Cl_2]-$. ${\Delta}-s-cis-[Rh(SS-eniba)Cl_2]^-$ has been utilized to react with S-methyl-L-cystcine(Smc) to give ${\Delta}-s-cis-[Rh(SS-eniba(Smc)]^+$. The oxidation of ${\Delta}-s-cis-[Rh(SS-eniba(Smc)]^+$ using $H_2O_2$ has produced ${\Delta}-s-cis-[Rh(SS-eniba)(Smc-o)]^+$, in which the coordinated sulfur has been converted into the sulfoxide group. In a separate series of experiments the S-methyl-L-cysteine is oxidized by $H_2O_2$ to give S-methyl-L-cysteine sulfoxide, which is then coordinated to ${\Delta}-s-cis-[Rh(SS-eniba)Cl2]^-$ to make the standard complet of ${\Delta}-s-cis-[Rh(SS-eniba)(Sme-o)]+$ for comparison with the complex obtained from the oxidation of ${\Delta}-s-cis-[Rh(SS-eniba)(Smc)]^+\;by\;H_2O_2.$

키워드

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