What Determines the Lewis Acidity of a Bismuthane? Towards Bi-Based FLPs

Aiming at intramolecular frustrated Lewis pairs (FLPs) based on soft Lewis acidic bismuth centers, a phosphine function was combined with a dichloridobismuthane unit on a phenylene backbone utilizing a scrambling approach. The reaction between two equivalents of BiCl₃ and (o-(Ph₂P)C₆H₄)₃Bi yielded (o-(Ph₂P)C₆H₄)BiCl₂(THF), the structure of which indicated Bi^…P interactions and thus a pronounced Lewis acidity at the bismuth center that was confirmed by the Gutmann-Beckett method. However, the system turned out to be insufficient to be utilized for FLP reactivity. Hence, the chloride ligands were exchanged by iodide and C₂F₅ substituents, respectively. Despite a lower electronegativity the iodide compound exhibits a shorter Bi^…P contact, while the C₂F₅ substituents led to a further decrease of the Lewis acidity, despite their high group electronegativity. DFT calculations rationalized this by a quenching of the Lewis acidity inherent to the σ*(Bi−C) orbital by negative hyperconjugation from occupied p-orbitals at the F atoms. Furthermore, it turned out that the strength of the covalent Bi−X σ-bond is a more important factor than the charge at Bi in determining the energetic accessibility and thus Lewis acidity of the antibonding σ*(Bi−C) orbital.