Rhodium-Mediated Functionalization of White Phosphorus:  A Novel Formation of C−P Bonds

The rhodium alkyl and aryl complexes [(tri-phos)Rh(R)(eta(2)-C2H4)] (R = Me (1), Et (2), Ph (3); tri-phos = MeC(CH2PPh2)(3)) react with white phosphorus in THF at room temperature to give the new complexes [(triphos)Rh(eta(1):eta(2)-P4R)] (R = Me (4), Et (5), Ph (6)). This reaction represents the first example in which a P-C bond is formed by starting from white phosphorus through the mediation of a transition-metal complex.