The PO) 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 degrees C results in the formation of the Pt(II) phenylacetylene 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)(NH2Ph)] [TEA] 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 C6D6 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., NC5F5) results in the formation of the dimer [((t)bpy)Pt(mu-NHPh)](2)[BAr'(4)](2). Solid state X-ray diffraction studies of the complexes [((t)bpy)Pt(Me)(NHPh), [((t)bpy)Pt(NH2Ph)(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.