Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Electrocatalytic Reduction of Dioxygen by New Water Soluble Cobalt(II) Tetrakis-(1,2,5,6-tetrafluoro-4-NN'N''-trimethylanilinium)-β-octabromoporphyrin in Aqueous Solutions

  • Published : 1999.09.20
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Abstract

New water soluble and highly electron deficient cobalt(II) tetrakis-(1,2,5,6-tertrafluoro-4-NN'N"-trimethyla-nilinium)-β-octabromoporphyrin [Co II (Br8TTFP)(Y)2] was synthesized and used for the electrocatalytic reduction of dioxygen. The first reduction of synthesized [Co II (Br8TTFP)(Y)2] involves one electron process to give metal centered [Co I (Br8TTFP)(Y)2]. The reduction of potential [E1/2 = -0.32 V] of [Co II (Br8TTFP)(Y)2] shifts positively 370 mV compared with that of [Co II (TTFP)(Y)2] due to the substituted bromide to β-pyrrole positions. The electrochemically reduced [Co I (Br8TTFP)(Y)2] binds dioxygen and catalytically reduces it to HOOH by 2e - transfer. Cyclic and hydrodynamic voltammetry at a glassy carbon electrode in dioxygen-saturated aqueous solutions are used to study the electrocatalytic pathway.

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