Catch and Release: Orbital Symmetry Guided Reaction Dynamics from a Freed "Tension Trapped Transition State".

Journal Article

The dynamics of reactions at or in the immediate vicinity of transition states are critical to reaction rates and product distributions, but direct experimental probes of those dynamics are rare. Here, s-trans, s-trans 1,3-diradicaloid transition states are trapped by tension along the backbone of purely cis-substituted gem-difluorocyclopropanated polybutadiene using the extensional forces generated by pulsed sonication of dilute polymer solutions. Once released, the branching ratio between symmetry-allowed disrotatory ring closing (of which the trapped diradicaloid structure is the transition state) and symmetry-forbidden conrotatory ring closing (whose transition state is nearby) can be inferred. Net conrotatory ring closing occurred in 5.0 ± 0.5% of the released transition states, in excellent agreement with ab initio molecular dynamics simulations.

Full Text

Duke Authors

Cited Authors

  • Wang, J; Ong, MT; Kouznetsova, TB; Lenhardt, JM; Martínez, TJ; Craig, SL

Published Date

  • December 2015

Published In

Volume / Issue

  • 80 / 23

Start / End Page

  • 11773 - 11778

PubMed ID

  • 26322681

Electronic International Standard Serial Number (EISSN)

  • 1520-6904

International Standard Serial Number (ISSN)

  • 0022-3263

Digital Object Identifier (DOI)

  • 10.1021/acs.joc.5b01493

Language

  • eng