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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 34, Number 2
JKCSEZ 34(2)
April 20, 1990

Title	Mechanisms for Aquation of trans-[CoETECl2]+ and cis-β-[CoTETCl2]+ and Isomerization of trans-[CoETEClOH2]2+ trans-[CoETECl2]+와 cis-β-[CoTETCl2]+ 착이온의 수화반응 및 trans-[CoETEClOH2]2+ 착이온의 이성질화반응의 메카니즘
Author	Jong-Jae Chung, Sung-Oh Bek 정종재, 백성오
Keywords
Abstract	몇 가지 온도와 압력 하에서 trans-[CoETECl2]+와 cis-β-[CoTETCl2]+ 착이온의 수화반응과 trans-[CoETEClOH2]2+착이온의 이성질화반응의 반응속도를 분광광도법으로 측정하여 이들 착물의 반응메카니즘을 규명하였다. trans-[CoETECl2]+와 cis-β-[CoTETCl2]+ 착이온의 수화반응에 대한 활성화엔트로피, △S^≠는 각각 4.0 eu 및 5.3 eu이고 활성화부피, △V^≠는 각각 -5.8 cm3mol-1 및 -6.6 cm3mol-1(40℃)이었다. 이들 데이타로부터 수화반응위 메카니즘은 해리(D)메카니즘으로 추정할 수 있었다. trans-[CoETEClOH2]2+ 착이온의 cis-β-[CoETEClOH2]2+ 로의 이성질화반응에 대한 활성화엔트로피, △S^≠와 활성화부피, △V^≠는 각각 9.5 eu 및 8.4 cm3mol-1(30℃)이었다. 이들 데이타로부터 이성질화반응의 메카니즘은 H2O가 해리된 후 이성질화가 일어나는 해리(D)메카니즘인 것으로 추정할 수 있었다. The rate constants for the aquation of trans-[CoETECl2]+ and cis-β-[CoTETCl2]+ and the isomerization of trans-[CoETEClOH2]2+ were measured by spectrophotometric method under various temperature and pressure conditions. For the aquations of trans-[CoETECl2]+ and cis-β-[CoTETCl2]+, the activation entropies are 4.0 eu and 5.3 eu respectively and the activation volumes are -5.8 cm3mol-1 and -6.6 cm3mol-1 at 40℃, respectively. From these data the dissociative mechanism involving trigonal bipyramid-type intermediate is proposed for the acquation reaction. For the isomerization of trans-[CoETEClOH2]2+ to cis-β-[CoETEClOH2]2+ the activation entropy is 9.5 eu and the activation volume is 8.4 cm3mol-1 at 30℃. The mechanism of isomerization may be considered as the dissociative mechanism with H2O-dissociation.
Page	117 - 122
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