title: Contribution to the chemistry of the Belousov-Zhabotinsky reaction. Products of the Ferriin-Bromomalonic acid and the Ferriin-Malonic acid reactions.
abstract: In the present mechanistic schemes of the ferroin-catalyzed oscillatory Belousov-Zhabotinsky (BZ) reaction the oxidation of the organic substrates (bromomalonic or malonic acid) by ferriin (the oxidized form of the catalyst) plays an important role. As the organic products of these reactions were not yet identified experimentally, they were studied here by an HPLC technique. It was found that the main organic oxidation product of bromomalonic acid is bromo-ethene-tricarboxylic acid (BrEETRA), the same compound that is formed when bromomalonic acid is oxidized by Ce4+ (another catalyst of the BZ reaction). Formation of BrEETRA is explained here by a new mechanism that is more realistic than the one suggested earlier. To find any oxidation product of malonic acid in the ferriin-malonic acid reaction was not successful, however. Neither ethane-tetracarboxylic acid (ETA) nor malonyl malonate (MAMA), the usual products of the Ce4+- malonic acid reaction, nor any other organic acid, not even CO2, was found as a product of the reaction. We propose that malonic acid is not oxidized in the ferriin-malonic acid reaction, and it plays only the role of a complex forming catalyst in a process where Fe3+ oxidizes mostly its phenantroline ligand.
authors.affiliation: EGIS Pharmaceuticals PLC, H-1106 Budapest, Hungary.
authors.forename: Laszló
authors.initials: L
authors.lastname: Hegedüs
authors.forename: Horst-Dieter
authors.initials: HD
authors.lastname: Försterling
authors.forename: Lavinia
authors.initials: L
authors.lastname: Onel
authors.forename: Maria
authors.initials: M
authors.lastname: Wittmann
authors.forename: Zoltan
authors.initials: Z
authors.lastname: Noszticzius
mesh_terms: D002563:Cerium / Q000737:chemistry; D005290:Ferric Compounds / Q000737:chemistry*; D008314:Malonates / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010618:Phenanthrolines / Q000737:chemistry*
chemical_list: D005290:Ferric Compounds; D008314:Malonates; D010618:Phenanthrolines; C517405:bromomalonic acid; C517404:ferriin; C001635:ferroin; D002563:Cerium; C030290:malonic acid