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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 33, Number 3
JKCSEZ 33(3)
June 20, 1989 

Electrochemical Properties of Oxygen Adducts Tetradentate Schiff Base Cobalt (Ⅱ) Complexes in Pyridine (Ⅲ)

Pyridine 용액에서 네자리 Schiff Base Cobalt (Ⅱ) 착물들의 산소첨가 생성물에 대한 전기화학적 성질 (제 3 보)
Ku Hyung Cho, Seong Seob Seo, Dong Chul Chon

조기형, 서성섭, 전동철
네자리 Schiff base cobalt(II) 착물로서 Co(SND) 및 Co(SOPD)을 합성하여 pyridine용액에서 산소를 반응시켜 산소첨가 생성물로서 [Co(SND)(Py)]2O2 및 [Co(SOPD)(Py)]2O2 을 합성하였다. 이 착물들은 원소분석과 cobalt 정량, IR spectra, T.G.A. 및 자화율을 측정하여 확인하였으며, 산소 : cobalt(Ⅱ) 착물의 결합비가 1:2이고, 네자리 Schiff base cobalt(Ⅱ)와 pyridine 및 산소가 6배위로 결합함을 알았다. 0.1M TEAP-pyridine 용액에서 순환전압전류법에 의한 Co(SND)(Py)2 및 Co(SOPD)(Py)2 들의 Co(Ⅱ)/Co(Ⅲ)와 Co(Ⅱ)/Co(Ⅰ) 산화환원 과정은 가역 및 준가역적으로 일어난다. 산소첨가 생성물의 착물들은 비가역적으로 일어나며, 이들의 산소에 대한 환원과정은 Epc = -0.96 ∼-1.03V에서, 산화과정은 Epa = -0.78 ∼-0.80V 범위에서 일어나며, 이들 산화환원 과정은 준가역적으로 일어남을 알았다.

Tetradentate Schiff base cobalt(Ⅱ) complex; Co(SND) and Co(SOPD) were synthesized, and these complexes were allowed to react with dry oxygen to form oxygen adducts cobalt(Ⅲ) complexes such as [Co(SND)(Py)]2O2 and [Co(SOPD)(Py)]2O2 in pyridine. These complexes have been identified by IR specta, T.G.A., magnetic susceptibilities measurements and elemental analysis. It has been found that the oxygen adducts coblat(Ⅲ) complexes have hexacoordinated octahedral configuration with tetradentate Schiff base cobalt(Ⅱ), pyridine and oxygen, and the mole ratio of oxygen to cobalt(Ⅱ) complexes are 1;2. The redox reaction processes of Co(SND)(Py)2 and Co(SOPD)(Py)2 complexes were investigated by cyclic voltammetry with glassy carbon electrode in 0.1M TEAP pyridine. The result of redox reaction processes of Co(Ⅲ)/Co(Ⅱ) and Co(Ⅱ)/Co(Ⅰ) for Co(SND)(Py)2 and Co(SOPD)(Py)2 complexes are reversible or quasi reversible process but oxygen adducts complexes are irreversible processes. Redox process for oxygen of oxygen adducts complexes was quasi reversible and redox range of potential was Epc = -0.96 ∼-1.03V and Epa = -0.78 ∼-0.80V.

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