Table 1. Calculated Bi···P Atomic Distances (d, Å) in [PS₃BiCl_n]^3–n (n = 0–3) and [PS₃Bi(ACN)₃]³⁺, bond valences (s, valence units), Wiberg bond indices (WBIs), AIM Charges (q, electron) and Net Charge Donation from the Ligand to the [BiCl_n]^3-n moiety (Δq Calculated As the Sum of Partial AIM Charges in the Ligand Fragment), Properties at the Bond Critical Point of Electron Density (ρ_bcp, e/ų), Laplacian of the Electron Density (∇²ρ_bcp, e/Å⁵), Total Electronic Energy Density (H, au), and Ratio of Potential and Kinetic Energy Density (|V|/G)^a.

^aThe gas-phase data without PCM for PS₃BiCl₃ are taken from ref (52). All data were obtained at the ωB97XD/cc-pVDZ(-PP) level of theory. The values obtained with the solvent model PCM are shown in italics.