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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 31, Number 6
JKCSEZ 31(6)
December 20, 1987 

 
Title
Studies on The Electrochemical Properties of Oxygen adducts Tetradentate Schiff Base Cobalt(Ⅱ) Complexes in DMSO (Ⅰ)

DMSO용액에서 네자리 Schiff Base Cobalt(Ⅱ) 착물들의 산소 첨가 생성물에 대한 전기화학적 성질에 관한 연구 (제 1 보)
Author
Ki-Hyung Chjo, Jin-Soon Chung, Heui-Suk Ham, Seoing-Seob Seo

조기형, 정진순, 함희석, 서성섭
Keywords
Abstract
네자리 schiff base cobalt(Ⅱ) 착물로서 Co(SED), Co(SND) and Co(SOPD)들을 합성하여 이들 착물들의 DMSO 용액에서 산소를 가하여 산소첨가 생성착물로 [Co(SED)(DMSO)]2O2, [Co(SND)(DMSO)]2O2 및 [Co(SOPD)(DMSO)]2O2들을 합성하였다. 이들의 원소분석과 Cobalt정량, IR-Spectra, T.G.A. 및 자화율을 측정하여 산소:cobalt(Ⅱ) 착물의 결합비가 1:2이고 네자리 schiff base cobalt(Ⅱ)와 DMSO 및 산소가 6배위 결합으로 주어짐을 알았으며 Co(SED), Co(SND) 및 Co(SOPD) 착물들의 0.1M TEAP-DMSO용액에서 순환전압-전류법에 의한 산화 환원 과정이 Co(SED) 및 Co(SOPD)는 Co(Ⅱ) / Co(Ⅲ)와 Co(Ⅱ) / Co(Ⅰ) 과정이 가역적으로 일어나고 Co(SND)는 Co(Ⅱ) / Co(Ⅲ)과정은 가역적이지만 Co(Ⅱ) / Co(Ⅰ) 과정은 비가역적이다. 또한 산소 첨가 생성물의 착물들은 0.1M TEAP-DMSO 용액에서 산소결합의 환원과정이 Epc = -0.80∼-0.89V에서 일어나고 이에 Couple인 산화과정은 Epa = -0.70∼-0.76V에서 준가역적으로 일어남을 알았다.

Tetradentate schiff base cobalt(Ⅱ) complexes; Co(SED), Co(SND) and Co(SOPD) have been prepared, these complexes have react with dry oxygen in DMSO to form oxygen adducts cobalt(Ⅲ) complexes; [Co(SED)(DMSO)]2O2, [Co(SND)(DMSO)]2O2 and [Co(SOPD)(DMSO)]2O2. It seems to be that the oxygen adducts cobalt(Ⅲ) complexes have heexa coordinated octahedral configration with tetradentate schiff base cobalt (Ⅱ), DMSO and oxygen, and the mole ratio of oxygen to cobalt(Ⅱ) complexes are 1 : 2, these complexes have been identified by IR-Spectra, T.G.A., magnetic susceptibilitis and elemental analysis of C.H.N. and Cobalt. The redox reaction process of Co(SED), Co(SND) and Co(SOPD) complexes was investigated by cyclic voltammetry with glassy carbon electrode in 0.1M TEAP-DMSO. The results of redox reaction process of Co(Ⅱ) / Co(Ⅲ) and Co(Ⅱ) / Co(Ⅰ) for cobalt(SED) and cobalt(SOPD) complexes and Co(Ⅱ) / Co(Ⅲ) process for cobalt(SND) complex are reversible process but Co(Ⅱ) / Co(Ⅰ) process of Cobalt(SND) complex is irreversible, and oxygen adduct complexes to quasi reversibly with oxygen should be very closed related to the redox potentials of range, Epc = -0.80∼-0.89V and Epa = -0.70∼-0.76V.

Page
542 - 554
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