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

The rhodium alkyl and aryl complexes [(triphos)Rh(R)(η 2 -C 2 H 4 )] (R = Me ( 1 ), Et ( 2 ), Ph ( 3 ); triphos = MeC(CH 2 PPh 2 ) 3 ) react with white phosphorus in THF at room temperature to give the new complexes [(triphos)Rh(η 1:η 2 -P 4 R)] (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.