Redox processes in the iron(III)/9,10-phenanthraquinone system

Inorganic Chemistry
Petr Milko, Jana Roithová

Abstract

With the use of the model complexes [(PQ)FeCl(CH(3)O)](+), [(phen)FeCl(CH(3)O)](+), and [(PQ)(phen)FeCl(CH(3)O)](+), where PQ is 9,10-phenanthraquinone and phen is 1,10-phenanthroline, the reactivity of phenanthraquinone in complexes with iron(III) is investigated. It is shown that 9,10-phenanthraquinone takes part in redox processes occurring at iron and thereby allows the oxidation of methanolate to formaldehyde. The oxidation is driven by the reduction of iron(III) to iron(II) and 9,10-phenanthraquinone to the semihydroquinone radical or semiquinolate, if the hydrogen atom is transferred from methanolate to chlorine rather than PQ. 1,10-Phenanthroline, on the other hand, acts as an innocent ligand, and the [(phen)FeCl(CH(3)O)](+) complex shows a typical two-state reactivity. The reactivity of [(PQ)(phen)FeCl(CH(3)O)](+) reveals that the hexacoordination of iron energetically facilitates the oxidation of methanolate, and therefore it is proposed that, in the presence of suitable reductants, the mixture of iron(III) and 9,10-phenanthraquinone can lead to the generation of the semihydroquinone radicals, species responsible for the toxicity of PQ. The fragmentation of [(PQ)(phen)FeCl(CH(3)O)](+) also demonstrates a strong bindin...Continue Reading

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Citations

Jun 6, 2012·Inorganic Chemistry·Manas Kumar BiswasPrasanta Ghosh
Jan 1, 2010·Acta Crystallographica. Section E, Structure Reports Online·Hoong-Kun FunYan Zhang
Jun 13, 2012·Journal of Mass Spectrometry : JMS·Lucie JašíkováJana Roithová
Dec 7, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Abhishek MandalGoutam Kumar Lahiri
Mar 12, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Manas Kumar BiswasPrasanta Ghosh

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