Intramolecular Aromatic 1,5-Hydrogen Transfer in Free Radical Systems.
Molecular orbital calculations of the hydrogen-atom transfer between the ortho positions of the rings of the o-benzophenone predict an activation free energy of 8.5 kcal/mol at 298 K. Using transition-state theory, the predicted rate of H-transfer is 7.9 x 10(6) mol(-)(1), or 4.0 x 10(-)(6) mol (-)(1), per ortho hydrogen, in excellent agreement with experimental reports. A similar H-transfer in the divinyl ketone radical is predicted to have a higher barrier by 1.4 kcal/mol despite the fact that the latter can more easily accommodate a wider C-H-C (142.3 degrees vs 135.2 degrees ) angle in the transition state. Critical stabilization it the TS for the benzophenone radical H-transfer appears to be the result of C-H.O H-bonding interactions between the oxygen and the ortho H's that are not involved in the H-transfer. These results are confirmed by the H.O distances and the overlap populations between the H and O orbitals.
Sordo
T. L.
TL
Department of Chemistry, City University of New York-Hunter College and The Graduate School, 695 Park Avenue, New York, New York 10021.
Dannenberg
J. J.
JJ