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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 41, Number 9
JKCSEZ 41(9)
June 20, 1997 

 
Title
Stereospecific Reaction of S,S-prodien(=1,9-bis(S)-prolyl-1,9-dioxo-2,5,8-triazanonane) (Ⅰ); Synthesis of Λ-α β(ffm)-[Co(S,S-prodien)H2O]ClO4

S,S-prodien(=1,9-bis(S)-prolyl-1,9-dioxo-2,5,8-triazanonane)의 입체특이성 반응 (Ⅰ):Λ-α β(ffm)-[Co(S,S-prodien)H2O]ClO4의 합성
Author
Bae-Wook Lee, Jin-Woo Kim, Dong-Jin Lee, Bong-Gon Kim, Chang-Eon Oh, Myung-Ki Doh*

이배욱,김진우,이동진,김봉곤,오창언,도명기
Keywords
Abstract
입체특이성 반응을 나타내는 키랄성 다섯자리 리간드,1,9-b따O-prolyl-1,9-dloxo-2,5,8·tnan-nonane(S,S-prodien}를 S-prollne과 d1라hylenetriamine(dlen)으로부터 합성하여 13C-NMR 스펙트럼으로 확인하고, CoC1z 6H2O와 반응시켜 적자색의 작물인 [C아∫&prodlen)Hz이C1O4를 합성하였다. 원소분석, 전자흡수스펙트럼, 13C-NMR스펙트럼 자료에 따라 S∵S-prodlen은 5자리로 배위되면서 중심의 dlen부분은 서c형태로 결합하고, 한자리 리간드인 HzO는 dlen에 있는 2차질소원자에 대하여 cㄵ 위치에 존재하는 α A⒲}형임을 알게되었다. 또한(J)스펙트럼에 따라 킬레이트된 리간드는 입체선택적으로 배위되어 λ킨A⑹}[CoCS-prodien)Hz이+의 절대구조를 갖는다고 생각하였다.

A chiral pentadentate ligand, 1,9-bis(S)-prolyl-1,9-dioxo-2,5,8-tri-azanonane, (S,S-prochen) which shows the stereospecific reaction was synthesized from the reaction of S-proline and diethylenetriamine (dien). The red-violet [Co(S,S-prodien)H2O]ClO4 was prepared by the oxidation of the aqueous solution dissolving COCl2·6H2O and S,S-prodien. Elemental analysis, electronic absorption spectroscopy, and 13C-NMR spectroscopy suggest that the geometrical structure of the Co(Ⅲ) complex to be an α β (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 α β (ffm)-[Co(S,S-prodien)H2O]ClO4 has the Λ-form.

Page
465 - 470
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