Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Stereospecific Reaction of S,S-prodien(= 1,9-bis(S)-prolyl-1,9-dioxo-2,5,8-triazanonane) (Ⅰ); Synthesis of ${\wedge}-{\alpha}{\beta}$(ffm)-[Co(S,S-prodien)$H_2O$]$ClO_4$

S,S-prodien(=1,9-bis(S)-prolyl-1,9-dioxo-2,5,8-triazanonane)의 입체특이성 반응(I); ${\wedge}-{\alpha}{\beta}$(ffm)-[Co(S,S-prodien)$H_2O$]$ClO_4$의 합성

  • Lee, Bae Wook (Department of Chemistry, Yeungnam University) ;
  • Kim, Jin Woo (Department of Chemistry, Yeungnam University) ;
  • Lee, Dong Jin (Department of Industrial Chemistry Kyungil Unversity) ;
  • Kim, Bong Gon (Department of Chemical Education, Gyeongsang National University) ;
  • Oh, Chang Eon (Department of Chemistry, Yeungnam University) ;
  • Doh, Myung Ki (Department of Chemistry, Yeungnam University)
  • 이배욱 (영남대학교 이과대학 화학과) ;
  • 김진우 (영남대학교 이과대학 화학과) ;
  • 이동진 (경일대학교 공업화학과) ;
  • 김봉곤 (경상대학교 화학교육과) ;
  • 오창언 (영남대학교 이과대학 화학과) ;
  • 도명기 (영남대학교 이과대학 화학과)
  • Published : 19970900
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Abstract

A chiral pentadentate ligand, 1,9-bis(S)-prolyl-1,9-dioxo-2,5,8-triaza-nonane, (S,S-prochen) which shows the stereospecific reaction was synthesized from the reaction of S-proline and diethylenetriamine (dien). The red-violet $[Co(SS-prodien)H_2O]ClO_4$ was prepared by the oxidation of the aqueous solution dissolving $CoCl_2{\cdot}6H_2O$ and S,S-prodien. Elemental analysis, electronic absorption spectroscopy, and $^{13}C-NMR$ spectroscopy suggest that the geometrical structure of the Co(III) complex to be an ${\alpha}{\beta}$ (ffm) form, where the dien moiety of the ligand chelates the metal center to comprise a facial isomer, and an aqua ligand coordinates a cis site to the secondary nitrogens of the dien. Based upon the CD spectroscopic analysis, it seems that the absolute configuration of the ${\alpha}{\beta}$(ffm)-$[Co(SS-prodien)H_2O]ClO_4$ has the ${\Lambda}$-form.

입체특이성 반응을 나타내는 키랄성 다섯자리 리간드, 1,9-bis(S)-prolyl-1,9-dioxo-2,5,8-triaza-nonane(S,S-prochen)를 S-proline과 diethylenetriamine (dien)으로부터 합성하여 $^{13}C-NMR$스펙트럼으로 확인하고, $CoCl_2{\cdot}6H_2O$와 반응시켜 적자색의 착물인 $[Co(SS-prodien)H_2O]ClO_4$ 를 합성하였다. 원소분석, 전자흡수스펙트럼, $^{13}C-NMR$스펙트럼 자료에 따라 S,S-prodian은 5자리로 배위되면서 중심의 dien부분은 fac형태로 결합하고, 한자리 리간드인 $H_2O$는 dien에 있는 2차질소원자에 대하여 cis 위치에 존재하는 ${\alpha}{\beta}$ (ffm)-형임을 알게되었다. 또한 CD스펙트럼에 따라 킬레이트된 리가드는 입체선택적으로 배위되어 ${\Lambda}$-${\alpha}{\beta}$ (ffm)-$[Co(SS-prodien)H_2O]^+$의 절대구조를 갖는다고 생각하였다.

Keywords

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