Right Answer for the Right Reason? Benchmarking Protocols and Pitfalls on a Ru-Metathesis Example.

A layered meta-benchmarking analysis was devised with the aim of illustrating how to produce an experimental/computational protocol for the method selection and estimation of Gibbs energies of catalytically prominent reactions. Our test subject involved the active-latent equilibrium through the cis-trans isomerism of two metathesis catalysts: mesitylene-Ru-SCF-Cl and diisopropylphenyl-Ru-SCF-Cl. The strategy was two-fold: first to perform a computational benchmark for the energies in the gas phase, followed by benchmarking the enthalpy and the Gibbs energy, including solvation and entropy, from experimental references.