Enthalpy-Controlled Insertion of a “Nonspectator” Tricoordinate Phosphorus Ligand into Group 10 Transition Metal–Carbon Bonds

Abstract

Insertion of a tricoordinate phosphorus ligand into late metal-carbon bonds is reported. Metalation of a P<^>P-chelating ligand (L1), composed of a nontrigonal phosphorous (i.e., P(III)) triamide moiety, P(N(o-N(Ar)C6H4)(2), tethered by a phenylene linker to a -PiPr(2) anchor, with group 10 complexes L2M(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 L1 with (cod)Pt-II(Me)(Cl) does not lead to a metallophosphorane but rather to the standard bisphosphine chelate (kappa(2) -L1)Pt(Me)(Cl). These divergent reactivities within group 10 are rationalized by reference to periodic variation in M-C bond enthalpies.