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Ruthenium Metallacycles Derived from 14-Electron Complexes. New Insights into Olefin Metathesis Intermediates

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journal contribution
posted on 20.12.2006, 00:00 by Anna G. Wenzel, Robert H. Grubbs
Ruthenium(IV) metallacycles derived from both ethylene and propene are reported. The propene-derived metallacycles represent the first observed examples of substituted ruthenacyclobutanes and offer new insight into the preferred stereochemical orientation about metathesis intermediates. In addition, a metallacycle possessing an unsymmetrical N-heterocyclic carbene (NHC) ligand was prepared and investigated to ascertain the dynamics of the NHC relative to the metallacycle ring. Metallacycles investigated were found to possess exchange cross-peaks between the α- and β-positions in the 2D NMR, indicating a dynamic structure. The implications of these results to the mechanism of ruthenium-catalyzed olefin metathesis are discussed.