Theoretical study of the thermal isomerization of fulvene to benzene Article

Madden, LK, Mebel, AM, Lin, MC et al. (1996). Theoretical study of the thermal isomerization of fulvene to benzene . 9(12), 801-810. 10.1002/(SICI)1099-1395(199612)9:12<801::AID-POC852>3.0.CO;2-D

cited authors

  • Madden, LK; Mebel, AM; Lin, MC; Melius, CF

authors

abstract

  • The potential energy surface for the thermal isomerization of fulvene to benzene was studied by modified Gaussian-2 (G2M) and the bond additivity-corrected fourth-order perturbation Møller-Plesset (BAC-MP4) methods. Three isomerization pathways were investigated. One involves the intermediate prefulvene by a concerted mechanism, which has a significantly higher barrier. The second, also involving prefulvene and cyclopenta-1,3-dienylcarbene intermediates, has a barrier of 84·0 kcal mol-1. The third, a multi-step pathway, includes bicyclo[3.1.0]hexa-1,3-diene and cyclohexadiene carbene intermediates. The activation energy of the multi-step pathway was calculated to be 74·3 kcal mol-1, which is 7-11 kcal mol-1 higher than the experimental value obtained by a brief very low-pressure pyrolysis (VLPP) study. RRKM calculations were performed on the multi-step pathway in order to determine the rate of isomerization. These theoretical results cast doubt on the validity of the VLPP data. © 1996 by John Wiley & Sons, Ltd.

publication date

  • January 1, 1996

start page

  • 801

end page

  • 810

volume

  • 9

issue

  • 12