Identification of Cyclohexadienyl Hydrides as Intermediates in Molybdenum‐Catalyzed Arene Hydrogenation

Autor: Gabriele Hierlmeier, Paolo Tosatti, Kurt Puentener, Paul J. Chirik
Rok vydání: 2022
Předmět:
Zdroj: Angewandte Chemie International Edition. 62
ISSN: 1521-3773
1433-7851
DOI: 10.1002/anie.202216026
Popis: Treatment of phosphino(imino)pyridine (PIP) molybdenum cyclooctadiene (COD) complexes [(PIP)Mo(COD)] with dihydrogen in the presence of benzene selectively furnished the molybdenum cyclohexadienyl hydrides [(PIP)MoH(η5-C6H7)], which are precatalysts for the hydrogenation of benzene to cyclohexane. [(PIP)MoH(η5-C6H7)] arises from a rarely observed insertion of benzene into a molybdenum-hydride bond, a key step in the molybdenum-catalyzed homogeneous hydrogenation of arenes. The reaction with toluene afforded a single isomer of the corresponding molybdenum cyclohexadienyl hydride while para-xylene instead predominantly formed the molybdenum η6-arene complex with the insertion product being a minor component. Addition of carbon monoxide to a cyclohexane-d12 solution of [(PIP)MoH(η5-C6H7)] liberated cyclohexadiene, providing experimental support for a higher kinetic barrier for the subsequent steps en route to cycloalkanes.
Databáze: OpenAIRE
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