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KMID : 1059519900340020117
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Journal of the Korean Chemical Society
1990 Volume.34 No. 2 p.117 ~ p.122
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Mechanisms for Aquation of trans-[CoETECl2]+ and cis-β-[CoTETCl2]+ and Isomerization of trans-[CoETEClOH2]2+
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Chung Jong-Jae
Baek Sung-Oh
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Abstract
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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.
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KEYWORD
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