Density functional theory study of C-H activation of arenes and alkanes with Cp*RhPMe3

ORGN 127

Robert G. Iafe, rgiafe@chem.ucla.edu and K. N. Houk, houk@chem.ucla.edu. Department of Chemistry and Biochemistry, University of California, Los Angeles, 405 Hilgard Avenue, Los Angeles, CA 90095
Density functional theory calculations have been carried out on the potential energy surface for the oxidative addition of rhodium(I) to C-H bonds. It was found that these oxidative addition reactions all proceed in a concerted fashion via a three-centered transition state. The geometrical characteristics of η2-benzene, phenyl hydride, and propyl hydride complexes were examined in some detail. Different pathways to the oxidative addition product from the 16-electron rhodium(I) fragment and benzene were studied. Computations suggest a η2-benzene complex as an intermediate for aryl C-H insertion. Further predictions are made with methyl hydride, ethylene hydride, and cyclopropyl hydride insertions to rhodium.

 

Process R&D, Physical Organic Chemistry, Heterocycles, Aromatics, Metal-Mediated Reactions
8:00 PM-10:00 PM, Sunday, March 25, 2007 Hyatt Regency Chicago -- Riverside Center, Poster

Division of Organic Chemistry

The 233rd ACS National Meeting, Chicago, IL, March 25-29, 2007