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

This review highlights the stoichiometric functionalization of both white phosphorus and naked P-4 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 eta(3)-P-3 or, mu,eta(3)-P-3 ligands: (ii) the transfer of a methyl group from molybdenum to eta(5)-P-5 ligands to yield a norbornadiene-like mu(3),eta(4):eta(1):eta(1)-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 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. (C) 2004 Elsevier B.V. All rights reserved.