Abstract
AbstractThe dioxygen reactivity of a series of TMPA‐based copper(I) complexes (TMPA=tris(2‐pyridylmethyl)amine), with and without secondary‐coordination‐sphere hydrogen‐bonding moieties, was studied at −135 °C in 2‐methyltetrahydrofuran (MeTHF). Kinetic stabilization of the H‐bonded [( TMPA)CuII(O2.−)]+ cupric superoxide species was achieved, and they were characterized by resonance Raman (rR) spectroscopy. The structures and physical properties of [( TMPA)CuII(N3−)]+ azido analogues were compared, and the O2.− reactivity of ligand–CuI complexes when an H‐bonding moiety is replaced by a methyl group was contrasted. A drastic enhancement in the reactivity of the cupric superoxide towards phenolic substrates as well as oxidation of substrates possessing moderate C−H bond‐dissociation energies is observed, correlating with the number and strength of the H‐bonding groups.
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