Facile and General Synthesis of Polyphosphane Polyoxides with (O)PCP(O) Linkages

Polyphosphane polyoxides with (O)PCP(O) linkages are powerful chelating agents for extraction of actinides from nuclear wastes. They are obtained either by the Michaelis–Arbuzov reaction of chloromethylphosphane oxides and phosphorus(III) esters, or by the reaction of phosphane oxide carbanions with chlorophosphanes. With the latter method, the addition of a phosphane oxide carbanion in excess allowed us to overcome a transmetallation reaction and thereby obtain polyphosphane polyoxides in good yields. The 1H-NMR spectra of the PCH2P groups show the influence of the different R groups attached to the phosphorus atoms. We determined the coupling constants and the chemical shifts of these spin systems.