Ruthenium metallacycles derived from 14-electron complexes. New insights into olefin metathesis intermediates |
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Authors: | Wenzel Anna G Grubbs Robert H |
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Institution: | Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA. |
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Abstract: | 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 alpha- and beta-positions in the 2D NMR, indicating a dynamic structure. The implications of these results to the mechanism of ruthenium-catalyzed olefin metathesis are discussed. |
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