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ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 37, Number 11
JKCSEZ 37(11)
October 20, 1993 |
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Title |
Hg2+-induced Aquation of trans-[Co(3,2,3-tet)X2]+ (3,2,3-tet = 4,7-diazadecane-1,10-diamine, X2 = Cl2, (NO2)Cl, Br2, (NO2)Br, and (NO3)2) Complexes in Aqueous Solution
수용액에서 Hg2+에 의한 trans-[Co(3,2,3-tet)X2]+ (3,2,3-tet =
4,7-diazadecane-1,10-diamine, X2 = Cl2, (NO2)Cl, Br2, (NO2)Br, (NO3)2) 착물의
아쿠아 반응 |
Author |
Doo Cheon Yoon, Chang Eon Oh, Myung Ki Doh
윤두천, 오창언, 도명기 |
Keywords |
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Abstract |
수용액상에서 Hg2+에 의한 trans-[Co(3,2,3-tet)X2]+ (3,2,3-tet = 4,7-diazadecane-1,10-diamine, X2 = Cl2, (NO2)Cl, Br2, (NO2)Br, (NO3)2) 착물의 아쿠아 반응이 연구되었다. 생성물을 확인하고 반응메카니즘을 추정하기 위하여 크로마토그래피를 사용하였고 전자흡수 스펙트럼을 측정하였다. 그 결과 네자리 리간드인 3,2,3-tet가 배위된 여러가지 trans-[Co(3,2,3-tet)X2]+ 착물은 각각 아쿠아된 trans-[Co(3,2,3-tet)(OH2)2]3+ 착물을 거쳐 cis-β-[Co(3,2,3-tet)(OH2)2]3+ 착물이 생성되었다. Hg2+에 의한 trans-[Co(3,2,3-tet)Cl2]+ 착물과 trans-[Co(3,2,3-tet)(NO2)Cl]+ 착물의 아쿠아 반응에 대한 메카니즘을 추정하기 위하여 속도론적 조사를 하였따. 그 결과 trans-[Co(3,2,3-tet)Cl2]+ 착물은 D(dissociative)-메카니즘으로 진행되었고, trans-[Co(3,2,3-tet)(NO2)Cl]+ 착물은 Id(interchange dissociative)-메카니즘으로 진행되었다. 그리고 입체화학적인 거동을 조사하기 위하여 라세미(R,R:S,S)3,2,3-tet 대신에 키랄성이 R,R인 3,2,3,-tet를 배위시킨 trans-[Co(R,R-3,2,3-tet)Cl2]+ 착물에 Hg2+를 용리시켰을 때 아쿠아 반응에 대한 원편광이색성(circular dichroism) 스펙트럼을 측정하여 그 절대구조를 확인한 결과 △-cis-β-[Co(R,R-3,2,3-tet)(OH2)2]3+ 착물이 생성되었다. Hg2+-induced aquation trans-[Co(3,2,3-tet)X2]+ (3,2,3-tet = 4,7-diazadecane-1,10-diamine, X2 = Cl2, (NO2)Cl, Br2, (NO2)Br, (NO3)2) complexes was investigated in aqueous solution. The products and the reaction mechanism were confirmed by chromatography, UV/Vis. spectrum, and circular dichroism (CD) spectrum. From the results, Hg2+-induced aquation of 3,2,3-tet system has been produced cis-β complex via trans complex. The kinetic studies on Hg2+-induced aquation of trans-[Co(3,2,3-tet)Cl2]+ complex and trans-[Co(3,2,3-tet)(NO2)Cl]+ complex were also carried out to study the reaction mechanism. The results show that trans-[Co(3,2,3-tet)Cl2]+ complex undergoes the D(dissociative)-mechanism and trans-[Co(3,2,3-tet)(NO2)Cl]+ complex Id(interchange dissociavite)-mechanism. In order to confirm steric course for the reaction mechanism, Hg2+-induced aquation on trans-[Co(R,R-3,2,3-tet)Cl2]+ complex to which chiral R,R-3,2,3-tet was coordinated instead of the racemic(R,R:S,S) 3,2,3-tet was used has been examined by CD spectrum. From the results, the final complex was confirmed to be △-cis-β-[Co(R,R-3,2,3-tet)(OH2)2]3+ complex indicating the chirality was retained through whole process. |
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951 - 960 |
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