Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Synthesis of Pentadentate Schiff Base Molybdenum(Ⅴ) Complexes and Their Electrochemical Properties in Aprotic Solvents

다섯자리 Schiff Base Molybdenum(Ⅴ) 착물들의 합성과 비수용매에서의 전기화학적 성질

  • 김선숙 (전남대학교 자연과학대학 화학과) ;
  • 최주형 (전남대학교 자연과학대학 화학과) ;
  • 최용국 (전남대학교 자연과학대학 화학과) ;
  • 정병구 (전남대학교 자연과학대학 화학과)
  • Published : 19940200
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Abstract

Pentadentate Schiff base molybdenum(Ⅴ) complexes such as [Mo(Ⅴ)O(Sal-DET)(NCS)] and [Mo(Ⅴ)O(Sal-DPT)(NCS)] were synthesized by Sabat method. The structure of these complexes were identified by elemental analysis, spectroscopy, and thermogravimetric analysis(T.G.A.). It was found that the mole ratio of Schiff base ligand to the complexes was found to be 1 : 1. The redox processes of the complexes were investigated by cyclic voltammetric and differential pulse polarographic technique in nonaqueous solvent containing 0. 1 M tetraethyl ammonium perchlorate(TEAP) as supporting electrolyte at glassy carbon electrode. It was found that diffusion controlled reduction processes of four steps with one electron were 2Mo(Ⅴ)$\rightleftarrow^{e-}$ Mo(Ⅴ)Mo(Ⅳ) $\longrightarrow^{e-}$ 2Mo(Ⅳ), Mo(Ⅳ) $\longrightarrow^{e-}$ Mo(Ⅲ) $\longrightarrow^{e-}$ Mo(Ⅱ)

다섯자리 Schiff base의 molybdenum(Ⅴ)착물로써 [Mo(Ⅴ)O(Sal-DET)(NCS)] 와 [Mo(Ⅴ)O(Sal-DPT)(NCS)]들을 Sabat법에 의해 합성하였다. 이들 착물들의 원소분석, IR-spectrum, UV-Vis spectroscopy 및 Thermogravimetric analysis(T.G.A.)곡선으로부터 리간드 대 금속의 몰비가 1:1착물임을 확인하였다. 0.1M tetraethyl ammonium perchlorate(TEAP)지지전해질을 포함한 비수용매에서 순환 전압-전류법과 시차펄스 폴라그래피에 의한 전기화학적 측정으로부터 이들 착물들은 dimer로 형성된 후, 일전자 전이의 확전자 전이의 확산지배적인 환원과정이 다음과 같이 네단계로 진행됨을 알았다. 2Mo(Ⅴ)$\rightleftarrow^{e-}$ Mo(Ⅴ)Mo(Ⅳ) $\longrightarrow^{e-}$ 2Mo(Ⅳ), Mo(Ⅳ)$\longrightarrow^{e-}$ Mo(Ⅲ) $\longrightarrow^{e-}$ Mo(Ⅱ)

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