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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 33, Number 2
JKCSEZ 33(2)
April 20, 1989 

 
Title
Electrochemical Reduction for trans-Complexes of Cobalt (Ⅲ) with Bis(ethylenediamine) and Monodendate Ligands

한자리 리간드를 포함하는 트란스비스 (에틸렌디아민) 코발트 (Ⅲ) 이온의 전극 환원반응
Author
Jung-Ui Hwang, Jong-Jae Chung, Jae-Duck Lee

황정의, 정종재, 이재덕
Keywords
Abstract
trans-[Co(en)2X2](ClO4)n의 전극환원 반응메카니즘(X : 시아나이드, 나이트라이트, 암모니아, 그리고 이소티오시아네이트)을 순환전압전류법 및 폴라로그래피법으로 조사하였다. 수은전극일 때 Co(Ⅲ)상태에서 Co(Ⅱ) 상태로 되는 확산지배적인 1전자 비가역반응 이후에 착물의 분광화학적 흡수파가 큰 시아나이드가 배위된 착물은 (en), CN-가 해리되지 않았으며 전극반응 생성물이 전극에 흡착되었고, NO2-, NH3는 해리되었다. 그 후 모든 Co(Ⅱ) 착물상태가 금속상태로 2전자 비가역 과정으로 환원되면서 (en)이 해리되었다. 수은전극에서 NO2-가 해리되는 속도가 57∼100m sec 이상으로 측정되었다. 탄소전극일 때 이들 착물의 첫단계 환원은 확산지배적인 1전자 비가역 과정이며 분광학적 흡수파수가 증가할 때 환원 피이크전위(-Ep)가 증가하였다.

Electrochemical reductions of trans-[Co(en)2X2](ClO4)n (where X is cyanide, nitrite, ammonia, and isothiocyanate) were investigated by cyclic voltammetry and polarography at mercury and glassy carbon electrode. trans-[Co(en)2(CN)2]ClO4 was reduced to Co(Ⅱ) complex followed by adsorption to the mercury electrode. Cyanide ion was not released from the reduced Co(Ⅱ) complex but the cyanide and (en) were released after the reduction to metallic cobalt. The other complexes except trans-[Co(en)2(CN)2]ClO4 were reduced to cobalt(Ⅱ) complexes followed by release of monodendate ligand, and (en) was released at the reduction step to metallic cobalt. trans-[Co(en)2(NO2)2]ClO4 was reduced to cobalt(Ⅱ) complex, and NO2- ion was released followed by electroreduction through ECE mechanism at pH 2. On glassy carbon electrode, all complexes of Co(Ⅲ) were reduced to Co(Ⅱ) complexes with irreversible one-electron diffusion controlled reaction in which (en) was not released at this step. Increasing absorption wave number of complexes caused to negative shift of peak potential.

Page
215 - 224
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