The Chemistry of a Non-Interacting Vicinal Frustrated Phosphane/Borane Lewis Pair

Abstract

The dimesitylphosphinocyclopentene/HB(C₆ F₅ )₂ -derived vicinal trans-1,2-P/B frustrated Lewis pair (FLP) 4 shows no direct phosphane-borane interaction. Toward some reagents it behaves similar to an intermolecular FLP; it cleaves dihydrogen, deprotonates terminal alkynes, and adds to organic carbonyl compounds including CO₂ . It shows typical intramolecular FLP reaction modes (cooperative 1,1-additions) to mesityl azide, to carbon monoxide, and to NO. The latter reaction yields a persistent P/B FLPNO nitroxide radical, which undergoes H-atom abstraction reactions. The FLP 4 serves as a template for the CO reduction by [HB(C₆ F₅ )₂ ] to generate a FLP-η² -formylborane. The formylborane moiety is removed from the FLP template by reaction with pyridine to yield a genuine pyridine stabilized formylborane that undergoes characteristic borane carbaldehyde reactions (Wittig olefination, imine formation). Most new products were characterized by X-ray diffraction.

Keywords: CO reduction; boron; dihydrogen splitting; frustrated Lewis pairs; nitroxide radicals; phosphorus.