Hierarchy of Commonly Used DFT Methods for Predicting the Thermochemistry of Rh-Mediated Chemical Transformations.

The accuracy and reliability of 17 commonly used density functionals in conjunction with Poisson-Boltzmann finite solvation model were gauged for predicting the free energy of Rh(I)- and Rh(III)-mediated chemical transformations such as ligand exchange, hydride elimination, dihydrogen elimination, chloride affinity, and silyl hydride bond activation reactions. In total, six Rh-mediated reactions were examined, and the computed density functional theory results were then subjected to comparison with the experimentally reported values. For reaction A, involving replacement of N with η-H over Rh(I), MPWB1K-D3, B3PW91, B3LYP, and BHandHYLP emerged to be the best functionals of all the tested methods in terms of their deviations ≤2 kcal mol from experimental data. For reaction B, in which exchange of η-CH with N over Rh(I) takes place, MPWB1K-D3 and M06-2X-D3 functionals performed the best, while as for reaction C (hydride elimination reaction in Rh(III) complex), it is PBE functional that showed impressive performance. Similarly, for reaction D (H elimination reaction in Rh(III) complex), PBE0-D3 and PBE-D3 showed exceptional results compared to other functionals. For reaction E (HO/Cl exchange), the PBE0 again shows impressive performance as compared to other functionals. For reaction F (Si-H activation), M06-2X-D3, PBE0-D3, and MPWB1K-D3 functionals are undoubtedly the best functionals. Overall, PBE0-D3 and MPWB1K-D3 functionals were impressive in all cases with lowest mean unsigned errors (3.2 and 3.4 kcal mol, respectively) with respect to experimental Gibbs free energies. Thus, these two functionals are recommended for studying Rh-mediated chemical transformations.