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

Abstract Biological oxygenation catalyzed by copper‐containing enzymes involves a dicopper O 2 adduct as the key intermediate. Significant insights were offered trans ‐1,2‐peroxodicopper intermediates. To understand activity of intermediate in oxygenation, series hydrogen‐bond‐assisted Cu I (L)−Cl and complexes [Cu −O ] 2+ investigated DFT computations. A reasonable two‐parameter structure‐activity model (R =0.8611) three‐parameter =0.8773) for chloride dissociation (ΔG 1 RXN ) established. The critical intramolecular out‐sphere hydrogen bonds assist formation stable complexes, which overcome steric hindrances electrostatic repulsion. An acceptable =0.7051) binding was obtained. fundamental interpretation bonding interactions provides an insight into modelling mimics.