A remarkable increase in the selectivity of four-electron reduction of O2 at an iron phthalocyanine complex adsorbed on a carbon electrode is accomplished by the use of a peroxo-bridged pyFeIIIPc-O2-PcFeIIIpy (py = pyridine, Pc = phthalocyanine dianion). Electroreduction of the dimer adsorbed on an electrode produced two solid state, cofacially fixed iron(II) phthalocyanine molecules under acidic conditions. Raman studies on the adsorbate revealed the restricted dynamics of the phthalocyanine rings adsorbed on a solid support that was responsible for the facile accommodation of an O2 molecule between the adjacent two iron(II) atoms. The contrast with the catalytic behavior of a mononuclear iron(II) stems from the formation of a μ-peroxo bond upon the reaction with O2, which subsequently cleaves under acidic conditions to produce two molecules of H2O.
|ジャーナル||Journal of the Chemical Society - Faraday Transactions|
|出版ステータス||Published - 1998 1 1|
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