Enthalpy-Controlled Insertion of a "Nonspectator" Tricoordinate Phosphorus Ligand into Group 10 Transition Metal-Carbon Bonds.
J Am Chem Soc
; 142(51): 21285-21291, 2020 Dec 23.
Article
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| ID: mdl-33306370
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 -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.
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01-internacional
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MEDLINE
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En
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J Am Chem Soc
Año:
2020
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Article