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Title: Catch and Release: Orbital Symmetry Guided Reaction Dynamics from a Freed “Tension Trapped Transition State”

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. In this paper, 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. Finally, net conrotatory ring closing occurred in 5.0 ± 0.5% of the released transition states, in excellent agreement with ab initio molecular dynamics simulations.
Authors:
 [1] ;  [2] ;  [1] ;  [2] ;  [3] ;  [1]
  1. Duke Univ., Durham, NC (United States). Dept. of Chemistry
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Materials Science Division
  3. Stanford Univ., CA (United States). Dept. of Chemistry
Publication Date:
Report Number(s):
LLNL-JRNL-663112
Journal ID: ISSN 0022-3263
Grant/Contract Number:
AC52-07NA27344; W911NF-07-0409
Type:
Accepted Manuscript
Journal Name:
Journal of Organic Chemistry
Additional Journal Information:
Journal Volume: 80; Journal Issue: 23; Journal ID: ISSN 0022-3263
Publisher:
American Chemical Society
Research Org:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Stanford Univ., CA (United States); Duke Univ., Durham, NC (United States)
Sponsoring Org:
USDOE; US Army Research Office (ARO)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1255180

Wang, Junpeng, Ong, Mitchell T., Kouznetsova, Tatiana B., Lenhardt, Jeremy M., Martínez, Todd J., and Craig, Stephen L.. Catch and Release: Orbital Symmetry Guided Reaction Dynamics from a Freed “Tension Trapped Transition State”. United States: N. p., Web. doi:10.1021/acs.joc.5b01493.
Wang, Junpeng, Ong, Mitchell T., Kouznetsova, Tatiana B., Lenhardt, Jeremy M., Martínez, Todd J., & Craig, Stephen L.. Catch and Release: Orbital Symmetry Guided Reaction Dynamics from a Freed “Tension Trapped Transition State”. United States. doi:10.1021/acs.joc.5b01493.
Wang, Junpeng, Ong, Mitchell T., Kouznetsova, Tatiana B., Lenhardt, Jeremy M., Martínez, Todd J., and Craig, Stephen L.. 2015. "Catch and Release: Orbital Symmetry Guided Reaction Dynamics from a Freed “Tension Trapped Transition State”". United States. doi:10.1021/acs.joc.5b01493. https://www.osti.gov/servlets/purl/1255180.
@article{osti_1255180,
title = {Catch and Release: Orbital Symmetry Guided Reaction Dynamics from a Freed “Tension Trapped Transition State”},
author = {Wang, Junpeng and Ong, Mitchell T. and Kouznetsova, Tatiana B. and Lenhardt, Jeremy M. and Martínez, Todd J. and Craig, Stephen L.},
abstractNote = {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. In this paper, 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. Finally, net conrotatory ring closing occurred in 5.0 ± 0.5% of the released transition states, in excellent agreement with ab initio molecular dynamics simulations.},
doi = {10.1021/acs.joc.5b01493},
journal = {Journal of Organic Chemistry},
number = 23,
volume = 80,
place = {United States},
year = {2015},
month = {8}
}