Impact of Intramolecular Hydrogen Bonding on the Reactivity of Cupric Superoxide Complexes with O-H and C-H Substrates.

ABSTRACT: The 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 [( ( X 1 ) ( X 2 ) TMPA)Cu^II (O₂ ^.- )]⁺ cupric superoxide species was achieved, and they were characterized by resonance Raman (rR) spectroscopy. The structures and physical properties of [( ( X 1 ) ( X 2 ) TMPA)Cu^II (N₃ ^- )]⁺ azido analogues were compared, and the O₂ ^.- reactivity of ligand-Cu^I complexes when an H-bonding moiety is replaced by a methyl group was contrasted. A drastic enh

SUBMITTER: Diaz DE 

PROVIDER: S-EPMC6878127 | biostudies-literature | 2019 Dec

REPOSITORIES: biostudies-literature