A computational Hammett analysis of oxy-insertion into platinum-aryl bonds is performed. Modeled transformations involve the two-step conversion of [((X)bpy)Pt(R)(OY)](+) (R = p- or m-X-C(6)H(4); Y = 4- or 3-X-pyridine; (X)bpy = 4,4'- or 5,5'-X-bpy; X = NO(2), H, OMe, NMe(2)) proceeding through a Pt-oxo intermediate to form aryloxide [((X)bpy)Pt(OR)(Y)](+), which contrasts a one-step non-redox ...
