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

Abstract

This review highlights the stoichiometric functionalization of both white phosphorus and naked P n fragments derived from the metal-mediated demolition of the P 4 tetrahedron. In a first section, the alkylation of P n ligands is discussed giving specific examples such as: (i) the electrophilic alkylation of η 3-P 3 or, μ,η 3-P 3 ligands: (ii) the transfer of a methyl group from molybdenum to η 5-P 5 ligands to yield a norbornadiene-like μ 3,η 4:η 1:η 1-MeP 7 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 P n 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 P n ligands which is a versatile, not yet completely explored, method to form an unprecedented variety of carbon–phosphorus heterocycles.