Coordination selectivity in the reaction of iron(II) with 8-hydroxy-7-(8-quinolyl)azo-5-quinolinesulfonic acid.
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The formation of an iron(II) complex with 8-hydroxy-7-(8-quinolyl)azo-5-quinolinesulfonic acid (QHQS,H<SUB>2</SUB>qhqs) has been investigated on the basis of the electronic absorption spectra, the equilibrium, and the stopped-flow kinetics in a 0.10 mol dm<SUP>−3</SUP> aqueous sodium chloride solution at 25°C with a view to elucidating the coordination selectivity of the ligand. A 1:2 (metal:ligand) complex forms in an acidic medium with a selective coordination of QHQS to iron(II), with its 2-(8-quinolylazo)phenol moiety acting as a terdentate ligand. The complex formation reaction proceeds through a single pathway of Fe<SUP>2+</SUP> with Hqhqs<SUP>−</SUP>, a ligand species singly protonated at the phenolate oxygen, with the rate constant (<I>k</I><SUB>21</SUB>) of <I>k</I><SUB>21</SUB>=(3.16±0.20)×10<SUP>5</SUP> mol<SUP>−1</SUP>dm<SUP>3</SUP>s<SUP>−1</SUP>, to form a mono-ligand complex as the rate-determining step. The coordination of the ligand by 8-quinolyl nitrogen, followed by a rate-determining bonding of phenolato oxygen, was suggested as the reaction mechanism.
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