Pt(II) and Pt(IV) amido, aryloxide, and hydrocarbyl complexes: synthesis, characterization, and reaction with dihydrogen and substrates that possess C-H bonds

The Pt(II) amido and phenoxide complexes ((t)bpy)Pt(Me)(X), ((t)bpy)Pt(X)(2), and ((t)bpy)Pt(X)(py)]BAr'(4)] (X = NHPh, OPh; py = pyridine) have been synthesized and characterized. To test the feasibility of accessing Pt(IV) complexes by oxidizing their Pt(II) precursors, the previously reported ((t)bpy)Pt(R)(2) (R = Me and Ph) systems were oxidized with I(2) to yield ((t)bpy)Pt(R)(2)(I)(2). The analogous reaction with ((t)bpy)Pt(Me)(NHPh) and MeI yields the corresponding ((t)bpy)Pt(Me)(2)(NHPh)(I) complex. Reaction of ((t)bpy)Pt(Me)(NHPh) and phenylacetylene at 80 °C results in the formation of the Pt(II) phenylacetylide complex ((t)bpy)Pt(Me)(C≡CPh). Kinetic studies indicate that the reaction of ((t)bpy)Pt(Me)(NHPh) and phenylacetylene occurs via a pathway that involves ((t)bpy)Pt(Me)(NH(2)Ph)]TFA] as a catalyst. The reaction of H(2) with ((t)bpy)Pt(Me)(NHPh) ultimately produces aniline, methane, (t)bpy, and elemental Pt. For this reaction, mechanistic studies reveal that 1,2-addition of dihydrogen across the Pt-NHPh bond to initially produce ((t)bpy)Pt(Me)(H) and free aniline is catalyzed by elemental Pt. Heating the cationic complexes ((t)bpy)Pt(NHPh)(py)]BAr'(4)] and ((t)bpy)Pt(OPh)(py)]BAr'(4)] in C(6)D(6) does not result in the production of aniline and phenol, respectively. Attempted synthesis of a cationic system analogous to ((t)bpy)Pt(NHPh)(py)]BAr'(4)] with ligands that are more labile than pyridine (e.g., NC(5)F(5)) results in the formation of the dimer ((t)bpy)Pt(μ-NHPh)](2)BAr'(4)](2). Solid-state X-ray diffraction studies of the complexes ((t)bpy)Pt(Me)(NHPh), ((t)bpy)Pt(NH(2)Ph)(2)]OTf](2), ((t)bpy)Pt(NHPh)(2), ((t)bpy)Pt(OPh)(2), ((t)bpy)Pt(Me)(2)(I)(2), and ((t)bpy)Pt(Ph)(2)(I)(2) are reported.