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Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
Direct observation of reaction intermediates for a well defined heterogeneous alkene metathesis catalyst
Frédéric Blanc1, Romain Berthoud, Christophe Copéret
1Institut de Chimie de Lyon, Ecole Supérieure Chimie Physique Electronique de Lyon/Centre National de la Recherche Scientifique/Université Lyon 1, Villeurbanne, France.
Abstract:
Grafting of [W([triple bond]NAr)(=CHtBu)(2,5-Me(2)NC(4)H(2))(2)] on a silica partially dehydroxylated at 700 degrees C (SiO(2- (700))) generates the corresponding monosiloxy complex [([triple bond]SiO)W([triple bond]NAr)(=CHtBu)(2,5-Me(2)NC(4)H(2))] as the major species (approximately 90%) along with [([triple bond]SiO)W([triple bond]NAr)(CH(2)tBu)(2,5-Me(2)NC(4)H(2))(2)], according to mass balance analysis, IR, and NMR studies. This heterogeneous catalyst displays good activity and stability in the metathesis of propene. Very importantly, solid state NMR spectroscopy allows observation of the propagating alkylidene as well as stable metallacyclobutane intermediates. These species have the same reactivity as the initial surface complex [([triple bond]SiO)W([triple bond]NAr)(=CHtBu)(2,5-Me(2)NC(4)H(2))], which shows that they are the key intermediates of alkene metathesis.
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