A Boryl-Substituted Diphosphene: Synthesis, Structure, and Reaction with n-Butyllithium To Form a Stabilized Adduct by p-p Interaction

A boryl-substituted diphosphene was synthesized through the nucleophilic borylation of PCl3 with a borylzinc reagent, followed by a reduction with Mg. A combined analysis of the resulting diboryldiphosphene by single-crystal X-ray diffraction, DFT calculations, and UV/Vis spectroscopy revealed a sigma-electron-donating effect for the boryl substituent that was slightly weaker than that of the 2,4,6-tri-tert-butylphenyl (Mes*) ligand. The reaction of this diboryldiphosphene with (BuLi)-Bu-n afforded a boryl-substituted phosphinophosphide that was, in comparison with the thermally unstable Mes*-substituted diaryldiphosphene, stabilized by a -electron-accepting effect of the boryl substituent.