Activation and Functionalization of White Phosphorus at Rhodium: Experimental and Computational Analysis of the [(triphos)Rh(h1:h2-P4RR')]Y Complexes [triphos = MeC(CH2PPh2)3; R = H, alkyl, aryl; R' = 2 electrons, H, Me)

The thermal reaction of white phosphorus with [(triphos)RhH3] in THF affords [(triphos)Rh(h1:h2-P4H)] (2), which contains the unprecedented tetraphosphido hydride ligand [triphos = MeC(CH2PPh2)3]. The related complexes [(triphos)Rh(h1:h2-P4R)] [R = Me;Et;Ph] are obtained at lower temperature by reaction of P4 and [(triphos)Rh(R)(h2-C2H4)] following ethane elimination. The hydrido(alkene) derivative [(triphos)Rh(H)(H2-C2H4)] does not afford 2 upon reaction with P4, but yields the tetraphosphido ethyl complex via a double insertion process.