Open AccessEnthalpy-Controlled Insertion of a “Nonspectator” Tricoordinate Phosphorus Ligand into Group 10 Transition Metal–Carbon Bonds
Author(s) -
Seung Jun Hwang,
Akira Tanushi,
Alexander T. Radosevich
Publication year - 2020
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.0c11161
Subject(s) - chemistry , metalation , ligand (biochemistry) , moiety , main group element , stereochemistry , transition metal , chelation , phosphorus , metal , insertion reaction , medicinal chemistry , enthalpy , crystallography , inorganic chemistry , organic chemistry , catalysis , biochemistry , physics , receptor , quantum mechanics
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)C 6 H 4 ) 2 , tethered by a phenylene linker to a -P i Pr 2 anchor, with group 10 complexes L 2 M(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 (κ 2 - L1 )Pt(Me)(Cl). These divergent reactivities within group 10 are rationalized by reference to periodic variation in M-C bond enthalpies.