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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 34, Number 1
JKCSEZ 34(1)
February 20, 1990 

Electrochemical Properties of Oxygen Adducts Pentadentate Schiff Base Cobalt (Ⅱ) Complexes in Aprotic Solvents

비수용매에서 다섯 자리 Schiff Base Cobalt (Ⅱ) 착물들의 산소 첨가 생성물에 대한 전기화학적 성질
Ki Hyung Chjo, Jin-Soon Chung, Yong-Kook Choi, Seong-Seob Seo

조기형, 정진순, 최용국, 서성섭
다섯 자리 Schiff base cobalt(Ⅱ) 착물로서 Co(Ⅱ)(Sal-DET)와 Co(Ⅱ)(Sal-DPT)들을 합성하여 비수용매에서 산소와 반응시켜 산소첨가 착물로서 [Co(Ⅲ)(Sal-DET)]2O2 및 [Co(Ⅲ)(DPT)]2O2들을 합성하였다. 이 착물들은 원소분석, IR spectra, TGA, DSC 및 자화율을 측정하여 확인하였으며, 비수용매에서 이들 착물들의 산소와의 몰결합비가 첫단계는 1:1이나 시간이 경과하면 고체상태에서와 같이 1:2로 가는 μ-peroxo형의 6배위 Cobalt(Ⅲ)착물들이 형성됨을 알았다. Co(Ⅱ)(Sal-DET)및 Co(Ⅱ)(Sal-DPT)와 이들 산소첨가 착물들의 0.1M TEAP-DMSO와 0.1M TEAP-pyridine 용액에서 순환전압-전류법 및 DPP법에 의한 환원과정은 두 단계로 일전자의 비가역적인 Co(Ⅲ)/Co(Ⅱ)와 Co(Ⅱ)/Co(Ⅰ)의 과정이 주어지나 산소첨가 착물에서 산소결합의 환원전위는 Epc = -0.97V∼-0.86V이고 이에 couple인 산화전위는 Epa = -0.87V ∼ 0.64V에서 일전자의 준가역적 산화환원 과정으로 일어남을 알았다.

Pentadentate Schiff base cobalt(Ⅱ) complexes; Co(Ⅱ)(Sal-DET) and Co(Ⅱ)(Sal-DPT) were synthesized and these complexes were allowed to react with dry to form oxygen adducts of cobalt(Ⅱ) complexes such as [Co(Ⅲ)(Sal-DET)]2O2 and [Co(Ⅲ)(DPT)]2O2 in aprotic solvents. These complexes have been identified by IR spectra, TGA, DSC, magnetic susceptibility measurements, and elemental analysis. It has been found that the oxygen adadduct complexes of μ-peroxo type have hexaccordinated octahedral configuration with pentadentate schiff base cobalt(Ⅱ) and oxygen, but the mole ratio of oxygen to cobalt(Ⅲ) complexes of first step for oxygen adduct formation reaction of cobalt(Ⅱ) complexes in aprotic solvents are 1:1. The redox reaction processes of Co(Ⅱ)(Sal-DET), Co(Ⅱ)(Sal-DPT), and oxygen adduct of cobalt(Ⅱ) complexes were investigated by cyclic voltammetry and DPP method with glassy carbon electrode in 0.1M TEAP-DMSO and 0.1M TEAP-pyridine. As a result the reduction reaction processes of Co(Ⅲ)/Co(Ⅱ) and Co(Ⅱ)/Co(Ⅰ) for cobalt(Ⅱ) complexes and oxygen adducts of cobalt(Ⅱ) complexes are two irreversible steps of one eletron process, and reaction processes of oxygen for oxygen adducts complexes were quasireversible and redox range of potential was Epc = -0.97V∼-0.86V and Epa = -0.87V ∼ 0.64V.

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