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

Gabriele Hierlmeier, Paolo Tosatti, Kurt Puentener, Paul J. Chirik

Research output: Contribution to journalArticlepeer-review

9 Scopus citations

Abstract

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 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.

Original languageEnglish (US)
Article numbere202216026
JournalAngewandte Chemie - International Edition
Volume62
Issue number3
DOIs
StatePublished - Jan 16 2023

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • Catalysis

Keywords

  • Arenes
  • Hydrides
  • Hydrogenation
  • Molybdenum
  • Reaction Mechanisms

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