Model Compounds of Ruthenium-alkene Intermediates in Olefin Metathesis Reactions

The development of a model system to study ruthenium-olefin complexes relevant to the mechanism of olefin metathesis is reported. Upon addition of 1,2-divinylbenzene to (H2IMes)(py2)(Cl)2Ru=CHPh (H2IMes = 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene), two ruthenium-olefin adducts are formed. On the basis of 1H NMR spectroscopy experiments and X-ray crystallographic analysis, these complexes are assigned as side-bound isomers in which the olefin and H2IMes ligands are coordinated cis to each other. The dynamic interconversion of these two ruthenium complexes was determined to have a barrier of 19.1 +/- 0.1 kcal/mol.