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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 35, Number 1
JKCSEZ 35(1)
February 20, 1991 

Electrochemical Properties of Binuclear Nickel(Ⅱ) and Copper(Ⅱ) Complexes with Tetradentate Schiff Base in Aprotic Solvents (1)

비수용매에서 이핵성 네자리 Schiff Base Nickel(Ⅱ) 및 Copper(Ⅱ) 착물들의 전기화학적 성질 (제 1 보)
Ki-Hyung Chjo, Yong-Kook Choi, Seong-Seob Seo, Song-Ju Lee

조기형, 최용국, 서성섭, 이송주
이핵성 네자리 Schiff base nickel(Ⅱ) 및 copper(Ⅱ) 착물로서 [Ni(Ⅱ)2(SMPD)2(L)2], [Ni(Ⅱ)2(SPPD)2(L)2], [Cu(Ⅱ)2(SMPD)2] 및 [Cu(Ⅱ)2(SPPD)2](L : Py, DMSO, DMF)들을 합성하여 원소분석, IR-spectrum, T.G.A, D.S.C 및 ESR을 측정하여 이핵성임을 확인하였다. 지지전해질로서 0.1M-TEAP을 포함한 비수용매(Py, DMSO 및 DMF)인 10mM-착물용액의 순환전압전류법과 DPP법으로 전기화학적 성질을 측정한 결과 일핵성인 Cu(Ⅱ)(SOPD) 및 Ni(Ⅱ)(SOPD)(L)2는 일전자의 확산지배적인 첫단계 환원과정이 0.1M TEAP-Py 용액에서는 비가역적이고, 0.1M TEAP-DMSO 용액에서는 가역 및 준가역적이고 0.1M TEAP-DMF 용액에서는 가역 및 E.C 반응으로 일어나지만, 이핵성 착물들은 일전자의 확산지배적인 환원과정이 두단계 과정으로 다음과 같이 일어남을 알았다.

We synthesized the binuclear Tetradentate Schiff base nickel(Ⅱ) and copper(Ⅱ) complexes ; [Ni(Ⅱ)2(SMPO)2(L)2], [Ni(Ⅱ)2(SPPD)2(L)2] and [Cu(Ⅱ)2(SMPD)2] and [Cu(Ⅱ)2(SPPD)2] (where, L : Py, DMSO and DMF). We identified the structure of these complexes by elemental analysis, IR-spectrum, T.G.A, D.S.C and ESR measurements. According to the results of cyclic voltammetry and DPP measurements in aprotic solvent included 0.1M TEAP as supporting electrolyte, we knew that diffusional controlled redox process of one step with one electron was irreversible process in 0.1M TEAP-Py solution. Also it was reversible or quasi reversible process in 0.1M TEAP-DMSO solution and reversible or E.C reaction mechanism in 0.1M TEAP-DMF solution at mononuclear complexes ; [Cu(Ⅱ)(SOPD)] and [Ni(Ⅱ)(SOPD)(L)2]. But, we knew that diffusional controlled redox process of two step for one electron of binuclear complexes was as follows. The values of redox potential for dimeric complexes in 0.1M TEAP-L solution (where, L ; Py, DMSO and DMF) with scan rate 100mV/sec.

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