Assessment of the computational protocol to predict standard reduction potential of Pt(IV) complexes

A broad benchmarking of the quantum mechanics (QM) protocols to predict the structure and reduction potential (epsilon o) of Pt(IV) complexes is presented. The basis set schemes, DFT methods, solvent effect, and conformational analysis are discussed for 11 distinct Pt(IV) complexes. As expected, the structure is not much sensitive to the QM protocol, being the average agreement with the X-ray data within 3%; however, when it comes to the epsilon o, the sensitivity is more significant, with just a few QM protocols accurately within 100 mV threshold. The protocol B3LYP/Pt-mDZP/jorge-DZP (P48) was the best choice, with a mean absolute deviation (MAD) of only 36 mV when the conformers with higher electrophilicity were considered. The P48 was validated for three Pt(IV) complexes not included in the original set of tests, leading to MAD = 24 mV.

Automated summary

A broad benchmarking of quantum mechanics (QM) protocols was conducted to predict the structure and reduction potential (epsilon o) of Pt(IV) complexes. The study discussed various factors such as basis set schemes, DFT methods, solvent effect, and conformational analysis for 11 distinct Pt(IV) complexes. Results showed that the structure was not highly sensitive to the QM protocol, with an average agreement of 3% with X-ray data. However, the reduction potential exhibited more significant sensitivity, with only a few QM protocols accurately within the 100 mV threshold. The protocol B3LYP/Pt-mDZP/jorge-DZP (P48) demonstrated the best performance, with a mean absolute deviation (MAD) of only 36 mV when considering conformers with higher electrophilicity. The P48 protocol was validated for three additional Pt(IV) complexes, resulting in a MAD of 24 mV.