Work

Quantum Chemical Studies of cis -[M(NH 3 ) 2 Cl 2 ] (M = Co I , Rh I , Ir I , Ni II , Pd II , Pt II , Cu III , Ag III , and Au III ): Structure, Bonding, and Hydrolysis

Year: 2026

Type: article

Abstract: High Resolution Image Download MS PowerPoint Slide 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(NH 3 ) 2 Cl 2 ] (M = Co I, Rh I, Ir I, Ni II, Pd II, Pt II, Cu III, Ag III, and Au III ), along with their bonding characteristics and hydrolysis behaviors. All complexes adopt a planar, four-coordinate geometry, with the d x 2 ‐ y 2 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(NH 3 ) 2 Cl 2 ] with M = Co I, Rh I, and Ir I were found to be unstable, exhibiting a tendency to form five-coordinated species. In contrast, cis -[M(NH 3 ) 2 Cl 2 ] complexes (M = Ni II, Pd II, Pt II, Cu III, Ag III, and Au III ) 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 -[Au III (NH 3 ) 2 Cl 2 ] + emerges as a potential candidate for antitumor applications.

Source: ACS Omega

DOI: 10.1021/acsomega.6c01898