Functionalization of white phosphorus in the coordination sphere of transition metal complexes

This review highlights the stoichiometric functionalization of both white phosphorus and naked Pn fragments derived from the metal-mediated demolition of the P4 tetrahedron. In a first section, the alkylation of Pn ligands is discussed giving specific examples such as: (i) the electrophilic alkylation of η3-P3 or, μ,η3-P3 ligands: (ii) the transfer of a methyl group from molybdenum to η5-P5 ligands to yield a norbornadiene-like μ3,η4:η1:η1-MeP7 ligand; (iii) the formation of P–C or P–H bonds mediated by rhodium and iron complexes; (iv) the use of ammonium salts to transfer an alkyl to polyphosphido clusters. Different methods to functionalise white phosphorus or other Pn ligands, including the cyclization of acrolein with diphosphenes and the insertion of CO or carbenes across P–P, P–M bonds, and P–E bonds (E = S, Se), are illustrated in appropriate sections. Finally, the last part of the article, reports on the astounding coupling of alkynes and phosphalkynes with Pn ligands which is a versatile, not yet completely explored, method to form an unprecedented variety of carbon–phosphorus heterocycles.