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 σ-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 (n) BuLi afforded a boryl-substituted phosphinophosphide that was, in comparison with the thermally unstable Mes*-substituted diaryldiphosphene, stabilized by a π-electron-accepting effect of the boryl substituent.

Ab oryl-substituted diphosphene was synthesized through the nucleophilic borylation of PCl 3 with ab orylzinc reagent, followed by areduction with Mg. Acombined analysis of the resulting diboryldiphosphene by single-crystal X-ray diffraction, DFT calculations,a nd UV/Vis spectroscopy revealed a s-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 n BuLi afforded ab oryl-substituted phosphinophosphide that was,i nc omparison with the thermally unstable Mes*substituted diaryldiphosphene,s tabilized by a p-electronaccepting effect of the boryl substituent.Scheme 1. Synthesis of diboryldiphosphene 2.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under http://dx.