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

ABSTRACT: 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 O(2)-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-η(2):η(2)-peroxodicopper(II) complexes, with stronger donors leading to more rapid formation and greater thermodynamic stability of product complexes [Cu(II) (2)((R)XYL)(O(2) (2-))](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

SUBMITTER: Karlin KD 

PROVIDER: S-EPMC3570229 | biostudies-literature | 2012 Jul

REPOSITORIES: biostudies-literature