Bleach catalysis in aqueous medium by iron(III)-isoindoline complexes and hydrogen peroxide

Abstract

Hydrogen peroxide and peroxymonocarbonate anion-based bleach reactions are important for many applications such as paper bleach, waste water treatment and laundry. Nonheme iron(III) complexes, $[\mathrm{Fe}^{\mathrm{III}}(\mathrm{L}^{1-4})\mathrm{Cl}_{2}]$ with the 1,3-bis($2^{\prime}$-Ar-imino)isoindolines ligands ($\mathrm{HL}^{n}$, $n=$1–4, Ar $=$ pyridyl, thiazolyl, benzimidazolyl and N-methylbenzimidazolyl, respectively) have been shown to catalyze the oxidative degradation of morin as a soluble model of a bleachable stain by $\mathrm{H}_{2}\mathrm{O}_{2}$ in buffered aqueous solution. In these experiments the bleaching activity of the catalysts was significantly influenced by the Lewis acidity and redox properties of the metal centers, and showed a linear correlation with the $\mathrm{Fe}^{\mathrm{III}}/\mathrm{Fe}^{\mathrm{II}}$ redox potentials (in the range of 197–415 mV) controlled by the modification of the electron donor properties of the ligand introducing various aryl groups on the bis-iminoisoindoline moiety. A similar trend but with low yields was observed for the disproportionation of $\mathrm{H}_{2}\mathrm{O}_{2}$ (catalase-like reaction) which is a major side reaction of catalytic bleach with transition metal complexes. The effect of bicarbonate ions might be explained by the reduction of Fe(III) ions and/or the formation of peroxymonocarbonate monoanion, which is a much stronger oxidant and could increase the formation of the catalytically active high-valent oxoiron species.

Keywords

• Iron complexes
• Isoindolines
• Catalase activity
• Bleach catalyst
• Hydrogen peroxide