Organophosphorus Synthesis beyond P-Cl Bond: The Development of Shelf-stable Reagents for [RP] Transfer

The direct chlorine-free incorporation of P1 units into organic molecules has very important synthetical value owing to environmental considerations and the prospect of accessing unique compounds with fascinating structures and useful properties. This selective survey presents a panorama of phosphorus species that are synthetic equivalents of free singlet phosphinidenes [R-P] and highlights the state-of-art of the [RP]-transfer reactions with emphasis on the synthesis of molecular architectures difficult to reach using traditional methods. Among stabilized phosphinidene precursors capable of RP-transfer are terminal transition-metal phosphinidene and phosphinidenoid complexes, dibenzo-7λ³- phosphinobornadienes, phosphinidene-phosphoranes, inversely polarized phosphaalkenes, phosphaketenes, intramolecularly base-stabilized phosphinidenes, (cyclo)polyphosphines and diphosphenes.