Olefin epoxidation and aliphatic or aromatic hydroxylation are often catalyzed by iron or manganese complexes with aminopyridine ligands. Hydrogen peroxide activation in these reactions is facilitated by carboxylic acids, which improve both efficiency and selectivity of catalytic oxidations. Rigidified diamine scaffolds improve the lifetime of the catalysts and may also effect catalytic activity and selectivity. In this work, reactions of rigid aminopyridine iron(II) or manganese(II) complexes with H2O2, H2O2/HOAc, or peroxyacids were studied by low-temperature stopped-flow kinetic methodology. The results confirm involvement of formally two-electron active oxidant(s) in hydrocarbon functionalization. Metal-bound peroxycarboxylates or peroxycarboxylic acids were identified as likely intermediates.

Kinetics and mechanisms of hydrocarbon oxidations with H2O2/HOAc catalyzed by iron and manganese complexes with rigid aminopyridine ligands

253rd National Meeting (2017)

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