Studies on Electroanalytical Chemistry for the Oxygen Adducted Tetradentate Schiff base Cobalt(III) Complexes in Pyridine Solution

Pyridine 용액에서 산소 첨가된 네자리 Schiff base Cobalt(III) 착물들의 전기 분석화학적 연구

Tetradentate Schiff base cobalt(II) complexes such as $Co(II)_2-N$, N-bis(salicylidene)-m-phenylendiimine; [$Co(II)_2(SMPD)_2(H_2O)_4$] and $Co(II)_2-N$, N-bis(salicylidene)-p-phenylendiimine: [$Co(II)_2(SPPD)_2(H_2O)_4$], and oxygen adducted cobalt (III) complexes such as [$Co(III)_2O_2(SMPD)_2(Py)_2$] and [$Co(III)_2O_2(SPPD)_2(Py)_2$] in pyridine solutions were synthesized. It was identified that the oxygen adducted cobalt(III) complexes have hexacoordinated octahedral configuration with pyridine and oxygen from the measurement of elemental analysis, AA, IR spectra, and TGA. The redox processes were investigated for the oxygen adducted complexes in 0.1M TEAP-pyridine solution, using cyclic voltammetry on the glassy carbon electrode. The redox processes of oxygen adducted Co(III) complexes result in $$[Co(III)_2-O_2-CO(III)]\rightarrow^{e^-}[Co(III)-O_2-Co(II)]\rightarrow^{e^-}[Co(II)-O_2-Co(II)]\rightleftarrows^{e^-}[Co(II)+Co(II)+O_2{\cdot}^-]\rightleftarrows^{e^-}[Co(II)+Co(I)+O_2{\cdot}^-]\rightleftarrows^{e^-}[Co(I)+Co(I)+O_2{\cdot}^-]$$.

네 자리 Schiff base cobalt(II) 착물로서 $Co(II)_2-N$, N-bis(salicylidene)-m-phenylendiimine : [$Co(II)_2(SMPD)_2(H_2O)_4$] 및 $Co(II)_2-N$, N-bis(salicylidene)-p-phenylendiimine : [$Co(II)_2(SPPD)_2(H_2O)_4$]들을 합성하였다. Pyridine 용액에서 이와 같은 착물들에 산소를 가하여 산소 첨가된 생성착물로서 [$Co(III)_2O_2(SMPD)_2(Py)_2$] 및 [$Co(III)_2O_2(SPPD)_2(Py)_2$]들을 합성하였다. 원소분석과 금속정량, IR spectia 및 TGA를 측정한 결과로부터 pyridine과 산소가 중심금속에 6배위로 결합함을 밝혔다. 0.1M TEAP-pyridine 용액에서 순환 전압-전류법에 의한 산소 첨가 생성 착물들의 산화-환원 과정은 다음과 같이 5단계의 일전자 반응으로 진행됨을 알았다. $$[Co(III)_2-O_2-CO(III)]\rightarrow^{e^-}[Co(III)-O_2-Co(II)]\rightarrow^{e^-}[Co(II)-O_2-Co(II)]\rightleftarrows^{e^-}[Co(II)+Co(II)+O_2{\cdot}^-]\rightleftarrows^{e^-}[Co(II)+Co(I)+O_2{\cdot}^-]\rightleftarrows^{e^-}[Co(I)+Co(I)+O_2{\cdot}^-]$$.