Reversible dioxygen binding and arene hydroxylation reactions: Kinetic and thermodynamic studies involving ligand electronic and structural variations

Copper–dioxygen interactions are of intrinsic importance in a wide range of biological and industrial processes. Here, we present detailed kinetic/thermodynamic studies on the O2-binding and arene hydroxylation reactions of a series of xylyl-bridged binuclear copper(I) complexes, where the effects of ligand electronic and structural elements on these reactions are investigated. Ligand 4-pyridyl substituents influence the reversible formation of side-on bound μ-η2:η2-peroxodicopper(II) complexes, with stronger donors leading to more rapid formation and greater thermodynamic stability of product complexes [CuII2(RXYL)(O22−)]2+. An interaction of the latter with the xylyl π-system is indicated. Subsequent peroxo electrophilic attack on the arene leads to C–H activation and oxygenation with hydroxylated products [CuII2(RXYLO–)(−OH)]2+ being formed. A related unsymmetrical binucleating ligand was also employed. Its corresponding O2-adduct [CuII2(UN)(O22−)]2+ is more stable, but primarily because the subsequent decay by hydroxylation is in a relative sense slower. The study emphasizes how ligand electronic effects can and do influence and tune copper(I)–dioxygen complex formation and subsequent reactivity.