Using DFT as a Guiding, Predicting and Explanatory Tool for the Study of Ruthenium based Olefin Metathesis Catalysts

Research spanning various DFT methodologies is a major part in many leading research groups around the globe, especially in catalysis. Thus, DFT calculations grow more efficient and can be adapted to perform high accuracy calculations for an array of chemical systems and phenomena. One can predict that before long, skilled experimentalists will use DFT as a complementary tool parallel to NMR, MS or any other characterization and analysis means. Publications¹ concerning ruthenium olefin metathesis catalysts, disclosing complementary experimental and calculated data are quite common; on the one hand results obtained from experimental work are empowered by theoretical analysis, on the other, and much more attractive, the theoretical predictions may lead to the development of new catalysts and properties which had escaped the insight of the experimentalists. Herein, two distinctive studies carried out in our group blending DFT and experimental research.

The first work deals with the nature of the anionic ligands in ruthenium pre-catalysts designed for asymmetric olefin metathesis.² DFT calculation were utilized to try to elucidate surprising results obtained while performing anionic ligand exchange in certain ruthenium complexes.

In a separate work, DFT was used to calculate the energy differences between cis/trans isomers with differing carbene ligands. This work is a part of a wider exploration on the influence of (cyclic alkyl amino carbene) CAAC sulfur – chelated ruthenium precatalysts for olefin metathesis.³

References:

1. Falivene, L.; Poater, A.; Cazin, C. S. J.; Slugovs, C.; Cavallo, L. Dalton.Trans. 2013, 42, 7312
2. Ivry, E.; Lemcoff, N. G.; unpublished
3. Rosenberg, I.; Lemcoff, N. G.; unpublished