On divorcing isomers, dissecting reactivity, and resolving mechanisms of propane CH and aryl CX (X = halogen) bond activations mediated by a ligated copper(III) oxo complex

摘要: Abstract The long suspected presence of two isomeric copper complexes (A and B), proportionally dependent on ESI cone voltage, was confirmed by their isolation, separation characterization in a travelling wave ion mobility spectrometry–mass spectrometer (TWIMS–MS) with modifications to allow for ion/molecule reactions be performed. Despite small difference cross-sectional area (∼1%) the isomers were well resolved, part due strong interaction isomer B N 2 buffer gas. reactivity each TWIMS-separated probed: propane reacted A via C H bond activation O-atom transfer, while no such observed B; aryl halides PhX (X = F, Cl, Br, I) also solely A, either concerted oxidation halide or transfer. DFT calculations reveal that X involves several mechanistic pathways.