Theoretical Investigation of Hydrogen‐Bond‐Assisted Tetradentate N4 Copper(I) Chloride andtrans‐1,2‐Peroxodicopper Complexes

Abstract

AbstractBiological oxygenation catalyzed by copper‐containing enzymes involves a dicopper O2adduct as the key intermediate. Significant insights were offered by thetrans‐1,2‐peroxodicopper intermediates. To understand the activity of thetrans‐1,2‐peroxodicopper intermediate in the oxygenation, a series of hydrogen‐bond‐assisted CuI(L)−Cl andtrans‐1,2‐peroxodicopper complexes [Cu2−O2]2+were investigated by DFT computations. A reasonable two‐parameter structure‐activity model (R2=0.8611) and a three‐parameter structure‐activity model (R2=0.8773) for chloride dissociation (ΔG1RXN) were established. The critical intramolecular out‐sphere hydrogen bonds assist the formation of stabletrans‐1,2‐peroxodicopper complexes, which overcome the steric hindrances and electrostatic repulsion. An acceptable two‐parameter structure‐activity model (R2=0.7051) for O2binding (ΔG2RXN) was obtained. The fundamental structure‐activity interpretation of the hydrogen bonding interactions provides an insight into the modelling oftrans‐1,2‐peroxodicopper mimics.