Phosphinophosphoranes: Mixed-Valent Phosphorus Compounds with Ambiphilic Properties

Herein, we present a simple synthesis of mixed-valent phosphinophosphoranes bearing three- and five-coordinate phosphorus centers. Compounds with phosphorus-phosphorus bonds were synthesized via a reaction of lithium phosphides RR'PLi with cat₂PCl (cat = catecholate), whereas derivatives with methylene-linked phosphorus centers were obtained via a reaction of phosphanylmethanides RR'CH₂Li with cat₂PCl. The presence of accessible lone-pair electrons on the P-phosphanyl atom of phosphinophosphoranes during the reaction of the title compounds with H₃B·SMe₂, where phosphinophosphorane-borane adducts were formed quantitatively, was confirmed. Furthermore, the Lewis basic and Lewis acidic properties of the phosphinophosphoranes in reactions with phenyl isothiocyanate were tested. Depending on the structure of the starting phosphinophosphorane, phosphinophosphorylation of PhNCS or formation of a five-membered zwitterionic adduct was observed. The structures of the isolated compounds were unambiguously determined by heteronuclear nuclear magnetic resonance spectroscopy and single-crystal X-ray diffraction. Moreover, by applying density functional theory calculations, we compared the Lewis basicity and nucleophilicity of diversified trivalent P-centers.