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-SCF3-Cl and diisopropylphenyl-Ru-SCF3-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. This “wedding cake” build-up of subsequent methods applied to our particular small test reaction indicates that: (1) DLPNO-CCSD(T)/CBS works well as a reference method for large systems. (2) Among several functionals ωB97XD and M06 were the most accurate. (3) Choosing between IEF-PCM and SMD solvation models turned out to be case dependent. (4) For the vibrational entropic component, low-frequency vibrations often produce humungous errors, which can be improved by Cramer and Truhlar’s or Grimme’s methods; however, their cut-off parameters had to be lowered from their standard values. (5) Solvation methods are important for enthalpies, but they are inadequate for entropies. (6) All of these components are equally important for the accuracy of organometallic complexes’ reactions. The only way to find the right method for the right reasons is to be sure to match all of the Gibbs energy terms to benchmarked experimental and computational values

Tuning the Latency by Anionic Ligand Exchange in Ruthenium Benzylidene Phosphite Complexes

Recently discovered cis-dichloro benzylidene phosphite complexes are latent catalysts at room temperature and exhibit exceptional thermal and photochemical activation behavior in olefin metathesis reactions. Most importantly, the study of these catalysts has allowed their introduction in efficient 3-D printing applications of ring-opening metathesis derived polymers and the control of chromatically orthogonal chemical processes. Moreover, their combination with plasmonic Au-nanoparticles has given rise to novel smart materials that are responsive to light. Given the importance of the ligand shell in the initiation and reactivity behavior of this family of complexes, we set out to investigate the effect of anionic ligand exchange. Thus, we report herein two new ruthenium benzylidene benzylphosphite complexes where the chloride anionic ligands have been replaced by bromide and iodide anions (cis-Ru-Phos-Br2 & cis-Ru-Phos-I2). The thermal and photochemical activations of these dormant catalysts in a variety of ring-closing and ring-opening metathesis polymerization (RCM and ROMP) reactions were thoroughly studied and compared with the previously known chloride precatalyst. Photochemical RCM studies provided similar results, especially in non-hindered reactions, with the UV-A wavelength being the best in all cases. On the other hand, the thermal activation profile exposed that the anionic ligand significantly affects reactivity. Notably, cis-Ru-Phos-I2 disclosed particularly impressive initiation efficiency compared to the other members of the family