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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 33, Number 5
JKCSEZ 33(5)
October 20, 1989 
 
Title
 Conversion of Coordinated Sulfur Atom into Sulfoxide Group via Oxidation Reaction of Metal Complexes of Tetradentates and Sulfur Amino Acids

네자리 리간드-황아미노산 금속착물의 산화반응에 의한 배위된 황원자의 sulfoxide 원자단으로의 전환
Author
 Sung Sil Lee, Peter P. Fu, Sung Rack Choi, Moo-Jin Jun

이숭실, Peter P. Fu, 최승락, 전무진
Keywords
Abstract
 주게원자가 질소원자와 산소원자인 N2O2형 네자리 리간드 ethylenediamine-N,N'-S-α-isobutylacetic acid(SS-eniba)의 디클로로 로듐(Ⅲ)[Rh(SS-eniba)Cl2]-의 합성에서 △-s-cis 및 Λ-uns-cis 이성체를 분리하였다. △-s-cis-[Rh(SS-eniba)Cl2]- 착물과 S-methyl-L-cystcine(Smc)의 반응으로부터 △-s-cis-[Rh(SS-eniba(Smc)]+ 착물을 합성한 다음 H2O2를 이용한 산화반응으로부터 배위된 황원자가 sulfoxide 원자단으로 산화된 △-s-cis-[Rh(SS-eniba)(Smc-o)]+(Smc-o=S-methyl-L-cysteine sulfoxide) 착물이 형성됨을 관찰하였다. 한편 S-methyl-L-cysteine을 H2O2와 반응시켜 sulfoxide 원자단으로 산화시킨 S-methyle-L-cysteine sulfoxide의 합성을 별도로 진행한 후 △-s-cis-[Rh(SS-eniba)Cl2]+ 착물에 배위시켜 표준착물인 △-s-cis-[Rh(SS-eniba)(Smc-o)]+를 합성한 다음 △-s-cis-[Rh(SS-eniba(Smc)]+ 착물을 산화시켜 얻은 △-s-cis-[Rh(SS-eniba)(Smc-o)]+ 착물과 비교하여 배위된 항원자가 sulfoxide 원자단으로 전환되었음을 또한 관찰하였다.

Reaction between the N2O2-type tetradentate ligand, ethylenediamine-N,N'-di-S-α-isobutylacetic acid (SS-emiba) and RhCl3·3H2O has yielded △-s-cis- and Λ-uns-cis-[Rh(SS-eniba)Cl2]-. △-s-cis-[Rh(SS-eniba)Cl2]- has been utilized to react with S-methyl-L-cystcine(Smc) to give △-s-cis-[Rh(SS-eniba(Smc)]+. The oxidation of △-s-cis-[Rh(SS-eniba(Smc)]+ using H2O2 has produced △-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 H2O2 to give S-methyl-L-cysteine sulfoxide, which is then coordinated to △-s-cis-[Rh(SS-eniba)Cl2]- to make the standard complet of △-s-cis-[Rh(SS-eniba)(Sme-o)]+ for comparison with the complex obtained from the oxidation of △-s-cis-[Rh(SS-eniba)(Smc)]+ by H2O2.
Page
 516 - 521
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