Impact of dielectric constant of solvent on the formation of transition metal‐ammine complexes

Abstract

The DFT‐level computational investigations into Gibbs free energies (ΔG) demonstrate that as the dielectric constant of the solvent increases, the stabilities of [M(NH3)n]2+/3+ (n = 4, 6; M = selected 3d transition metals) complexes decrease. However, there is no observed correlation between the stability of the complex and the solvent donor number. Analysis of the charge transfer and Wiberg bond indices indicates a dative‐bond character in all the complexes. The solvent effect assessed through solvation energy is determined by the change in the solvent accessible surface area (SASA) and the change in the charge distribution that occurs during complex formation. It has been observed that the SASA and charge transfer are different in the different coordination numbers, resulting in a variation in the solvent effect on complex stability in different solvents. This ultimately leads to a change between the relative stability of complexes with different coordination numbers while increasing the solvent polarity for a few complexes. Moreover, the findings indicate a direct relationship between ΔΔG (∆Gsolvent‐∆Ggas) and ΔEsolv, which enables the computation of ΔG for the compounds in a particular solvent using only ΔGgas and ΔEsolv. This approach is less computationally expensive.

Trends in the stability of covalent dative bonds with variable solvent polarity depend on the charge transfer in the Lewis electron-pair system

“…Previously, we studied complexes with covalent dative bonds in both neutral and charged systems and observed varying stability trends in solvents as the dielectric constants of the solvents changed. [5][6][7][8][9][10][11][12] We have shown that the stability of DB in neutral complexes increases systematically with increasing solvent polarity. [5][6][7][8][9][10] However, the opposite trend is observed for DB in charged coordinate complexes.…”

“…[5][6][7][8][9][10] However, the opposite trend is observed for DB in charged coordinate complexes. 11,12 The effect of solvent was also studied in hydrogen-bonded complexes. As expected, a decrease in stability with increasing solvent polarity was observed in most complexes.…”