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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 34, Number 5
JKCSEZ 34(5)
October 20, 1990 
 
Title
 The Aquation of Co(Ⅲ) Complexes in Pure Water and Mixed Water-Organic Solvents With Hg2+

수용액 및 물-유기용매 혼합용매에서의 Hg2+ 에 의한 Co(Ⅲ) 착물의 수화반응
Author
 Chang Eon Oh, Doo Cheon Yoon, Myung Ki Doh

오창언, 윤두천, 도명기
Keywords
Abstract
 촉매로서 Hg2+을 사용한 수화반응에서 cis-[Co(en)2(OH2)Cl]2+, [Co(NH3)5Cl]2+, cis-[Co(NH3)4(OH2)Cl]2+ 및 [Co(NH2CH3)5Cl]2+착물들은 Hg2+의 농도가 증가할수록 관측속도상수(kobs)의 값이 증가하였다. Hg2+에 의한 수화반응의 속도법칙은 Rate = k2K[complex][Hg2+]이었고, 그 메카니즘이 연구되었다. 또한 여러가지 유기용매-물 혼합용매에서 Co(Ⅲ)착물의 Hg2+에 의한 수화반응이 연구되었다. 용매의 성질인 Y (solvent ionizing power)값에 대한 log k를 도시하여 그 기울기인 m값을 얻었다. 그 m값으로부터 수화반응의 메카니즘을 추정하였다. 속도론적인 자료로부터 Hg2+에 의한 Co(Ⅲ)착물의 수화반응이 Id-메카니즘으로 제안되었다. 각 Co(Ⅲ)착물의 속도의 차이는 여러가지 리간드가 배위된 Co(Ⅲ)착물의 리간드장파라메타(Δ)값과 관계가 있었다.

Observed rate constants (kobs) for Hg2+-catalysed aquation of cis-[Co(en)2(OH2)Cl]2+, [Co(NH3)5Cl]2+, cis-[Co(NH3)4(OH2)Cl]2+, and [Co(NH2CH3)5Cl]2+ were measured at various concentrations of Hg2+. The kobs was increased with increasing the concentrations of Hg2+. The kobs were related to mechanistically derived rate constants by the relationship; Rate = k2K[complex][Hg2+]. Various mixed aqueous-organic solvent have been successfully employed for Hg2+-catalysed aquation of octahedral myetal complexes. From the slope of the plot of log k againt Y (solvent ionizing power), the mechanism on the aquation of Co(Ⅲ) complexes by Hg2+ has been suggested to be Id-mechanism. The change in a rate on aquation of each Co(Ⅲ) complex was related to the ligand field parameters (Δ), for Co(Ⅲ) complexes.
Page
 438 - 444
Full Text
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