Département de chimie moléculaire

We report a detailed investigation of the formation and self-decompn. of Cu(II)-hydroperoxo intermediates under the influence of second-coordination-sphere features provided by a cryptand. In soln., an equil. between two copper complexes with square-planar and square-pyramidal geometries was identified. Upon addn. of H2O2/Et3N, two copper(II)-hydroperoxo intermediates formed at different rates. Their decompn. via self-oxidn. was probed by deuterating select positions on the cryptand. This led to a small kinetic isotope effect of 1.5. Mass spectrometry anal. of the demetallated org. products is consistent with a direct oxygen-atom transfer to a tertiary amine on the cryptand, forming an N-oxide, unlike other models of copper mononuclear monooxygenase enzymes. [on SciFinder(R)]