Synthesis and characterization of the monomeric complex ('bpy)Pt(Me)(NHPh) ('bpy = 4,4'-di-tert-butyl-2,2'-dipyridyl) has been accomplished. Mechanistic studies reveal that 1,2-addition of dihydrogen across the Pt-anilido bond to initially produce ('bpy)Pt(Me)(H) and free aniline is catalyzed by elemental Pt rather than through a pathway that involves direct activation of H-2 by Pt and 1,2-addition across the Pt-NHPh bond.