Dehydrocoupling of phosphine–boranes using the [RhCp*Me(PMe3)(CH2Cl2)][BArF4] precatalyst: stoichiometric and catalytic studies

Abstract

We report a detailed, combined experimental and computational study on the fundamental B–H and P–H bond activation steps involved in the dehydrocoupling/dehydropolymerization of primary and secondary phosphine–boranes, H₃B·PPhR′H (R = Ph, H), using [RhCp*(PMe₃)Me(ClCH₂Cl)][BAr^F₄], to either form polyphosphino-boranes [H₂B·PPhH]_n (M_n ∼ 15 000 g mol⁻¹, PDI = 2.2) or the linear diboraphosphine H₃B·PPh₂BH₂·PPh₂H. A likely polymer-growth pathway of reversible chain transfer step-growth is suggested for H₃B·PPhH₂. Using secondary phosphine–boranes as model substrates a combined synthesis, structural (X-ray crystallography), labelling and computational approach reveals: initial bond activation pathways (B–H activation precedes P–H activation); key intermediates (phosphido-boranes, α-B-agostic base-stabilized boryls); and a catalytic route to the primary diboraphosphine (H₃B·PPhHBH₂·PPhH₂). It is also shown that by changing the substituent at phosphorus (Ph or Cy versus^tBu) different final products result (phosphido-borane or base stabilized phosphino-borane respectively). These studies provide detailed insight into the pathways that are operating during dehydropolymerization.