Enthalpy-Controlled Insertion of a "Nonspectator" Tricoordinate Phosphorus Ligand into Group 10 Transition Metal-Carbon Bonds.

Insertion of a tricoordinate phosphorus ligand into late metal-carbon bonds is reported. Metalation of a P^P-chelating ligand (), composed of a nontrigonal phosphorous (i.e., P(III)) triamide moiety, P(N(-N(Ar)CH), tethered by a phenylene linker to a -PPr anchor, with group 10 complexes LM(Me)Cl (M = Ni, Pd) results in insertion of the nontrigonal phosphorus site into the metal-methyl bond. The stable methylmetallophosphorane compounds thus formed are characterized spectroscopically and crystallographically. Metalation of with (cod)Pt(Me)(Cl) does not lead to a metallophosphorane but rather to the standard bisphosphine chelate (κ-)Pt(Me)(Cl). These divergent reactivities within group 10 are rationalized by reference to periodic variation in M-C bond enthalpies.