Ligand exchange at tetra-coordinated beryllium centres

Abstract

Mono and dinuclear phosphine complexes of beryllium halides [(PMe₃)₂BeX₂], [(PMe₃)BeX₂]₂ and [(PCy₃)BeX₂]₂ (X = Cl, Br, I) were synthesised and characterised via NMR and IR spectroscopy as well as single crystal X-ray diffraction experiments. Dissociation and ligand exchange processes at these complexes were investigated through variable temperature NMR experiments in combination with line shape analysis and complemented by quantum chemical calculations. The PMe₃ dissociation energy is smallest in [(PMe₃)₂BeCl₂], while PMe₃ exchange is similar in energy in all mononuclear [(PMe₃)₂BeX₂] complexes and follows an interchange mechanism. While [(PMe₃)BeX₂]₂ dissociates homolytically, [(PCy₃)BeX₂]₂ cleaves one phosphine ligand. These distinctive dissociation processes account for the different chemical behaviour of these complexes.