To gain molecular-level insights into cisplatin and its metal analogs, we performed a comprehensive investigation of the geometric and electronic structures of cis-M(NH3)2Cl2 (M = CoI, RhI, IrI, NiII, PdII, PtII, CuIII, AgIII, and AuIII), along with their bonding characteristics and hydrolysis behaviors. All complexes adopt a planar, four-coordinate geometry, with the dx2‐y2 orbital predominantly involved in ligand interactions. EDA-NOCV analyses indicate that the total interaction energy increasing from Group 9 to 11 with σ-interactions dominates the metal–ligand bonding. cis-M(NH3)2Cl2 with M = CoI, RhI, and IrI were found to be unstable, exhibiting a tendency to form five-coordinated species. In contrast, cis-M(NH3)2Cl2 complexes (M = NiII, PdII, PtII, CuIII, AgIII, and AuIII) undergo ligand exchange reactions via penta-coordinate trigonal-bipyramidal-like transition states. Their monoaquated derivatives all demonstrated high reactivity toward guanine. Considering their hydrolysis behaviors, cis-AuIII(NH3)2Cl2+ emerges as a potential candidate for antitumor applications.
Fu et al. (Sat,) studied this question.