Competition between concerted and stepwise dynamics in the triplet Di-π-methane rearrangement

  1. Jiménez-Osés, G. 1
  2. Liu, P. 1
  3. Matute, R.A. 1
  4. Houk, K.N. 1
  1. 1 University of California Los Angeles
    info

    University of California Los Angeles

    Los Ángeles, Estados Unidos

    ROR https://ror.org/046rm7j60

Revista:
Angewandte Chemie International

ISSN: 1433-7851

Año de publicación: 2014

Volumen: 53

Número: 33

Páginas: 8664-8667

Tipo: Artículo

DOI: 10.1002/ANIE.201310237 SCOPUS: 2-s2.0-84905717908 WoS: WOS:000340523500018 GOOGLE SCHOLAR

Otras publicaciones en: Angewandte Chemie International

Resumen

The molecular dynamics of the triplet-state Zimmerman di-π-methane rearrangement of dibenzobarrelene were computed with B3LYP and M06-2X density functionals. All productive quasiclassical trajectories involve sequential formation and cleavage of C-C bonds and an intermediate with lifetimes ranging from 13 to 1160 fs. Both dynamically concerted and stepwise trajectories are found. The average lifetime of this intermediate is significantly shorter than predicted by either transition-state theory or the Rice-Ramsperger-Kassel-Marcus model, thus indicating the non-statistical nature of the reaction mechanism. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.