A planar complex, [Rh(bpy)(2)](+) (bpy = 2,2’-bipyridine), was obtained from [Rh(ox)(bpy)(2)](+) (ox = oxalato) by photoirradiation. A rate constant k for the photoreaction was evaluated as 1 x 10(8) s(-1) in simple first-order kinetics, whereas a ligand dissociation, a reorganization of the coordinated bpy, and a two-electron transfer were involved in the reaction. The process of the Rh(I) complex generation was investigated in terms of a discrete variational (DV)-X alpha molecular orbital calculation on [Rh(ox)(HN=CHCH=NH)(2)](+) instead of [Rh(ox)(bpy)(2)](+). From the calculation, using the transition-state method, it was predicted that a transition of the ox pi* orbital to the metal 4d(z2) orbital caused the Ligand dissociation and the reorganization of the coordinated bpy occurred in the ox pi to Rh 4d(x2-y2) excited state stabilized by the ox elimination. Upon release of the ligand and a change from octahedral to square-planar geometry, the electron density on the metal increased and the Rh 4d orbital acquired a d(8) electronic configuration.