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| - Regarding the Mechanism of Olefin Metathesis withSol−Gel-Supported Ru-Based Complexes Bearing a BidentateCarbene Ligand. Spectroscopic Evidence for Return of thePropagating Ru Carbene
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| - Two isotopically and structurally labeled Ru-based carbenes (2-d4 and 13) have been preparedand attached to the surface of monolithic sol−gel glass. The resulting glass-supported complexes (18-dnand 19) exhibit significant catalytic activity in promoting olefin metathesis reactions and provide productsof high purity. Through analysis of the derivatized glass pellets used in a sequence of catalytic ring-closingmetathesis reactions mediated by various supported Ru carbenes, it is demonstrated that free Ru carbeneintermediates in solution can be scavenged by support-bound styrene ether ligands prior to the onset ofcompeting transition metal decomposition. The observations detailed herein provide rigorous evidence thatthe initially proposed release/return mechanism is, at least partially, operative. The present investigationsshed light on a critical aspect of the mechanism of an important class of Ru-based metathesis complexes(those bearing a bidentate styrene ether ligand).
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