1374112-69-2Relevant academic research and scientific papers
Synthesis and properties of bimetallic Hoveyda-Grubbs metathesis catalysts
Grudzien, Krzysztof,Malinska, Maura,Barbasiewicz, Michal
scheme or table, p. 3636 - 3646 (2012/07/13)
The catalytic activity of ruthenium Hoveyda-Grubbs complexes in olefin metathesis is a function of complex steric and electronic effects acting on initiation and propagation steps. In order to study the π-electron factors influencing the initiation process, we attempted syntheses of bimetallic complexes with common organic ligands bearing two chelate rings. While most of the studied ligand exchange reactions of the isomeric bis-chelating benzene derivatives gave mixtures of unstable complexes, a homodinuclear derivative of 1,4-dimethoxy-2,5-divinylbenzene was sparingly soluble and precipitated from the reaction mixture in a pure form. The complex was studied with spectroscopic and X-ray methods, which confirmed the symmetrical bimetallic structure. However, in model metathesis reactions the catalyst displayed activity very comparable to the related monometallic complexes. This suggests that in the bimetallic system two consecutive initiation processes of the metathesis catalyst (first, bimetallic complex + olefin → monometallic complex + propagating species; second, monometallic complex + olefin → styrene + propagating species) proceed at similar rates and, thus, no cooperativity between the two steps is displayed. Properties of the family of bimetallic complexes were probed with NMR studies, and π-electronic effects operating in the systems were discussed.
