Enthalpy-Controlled Insertion of a “Nonspectator” Tricoordinate Phosphorus Ligand into Group 10 Transition Metal–Carbon Bonds
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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 −PiPr2 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)PtII(Me)(Cl) does not lead to a metallophosphorane but rather to the standard bisphosphine chelate (κ2-L1)Pt(Me)(Cl). These divergent reactivities within group 10 are rationalized by reference to periodic variation in M–C bond enthalpies.
