Catch and Release: Orbital Symmetry Guided Reaction Dynamics from a Freed “Tension Trapped Transition State”
Abstract
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:
-
- Duke Univ., Durham, NC (United States). Dept. of Chemistry
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Materials Science Division
- Stanford Univ., CA (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Stanford Univ., CA (United States); Duke Univ., Durham, NC (United States)
- Sponsoring Org.:
- USDOE; US Army Research Office (ARO)
- OSTI Identifier:
- 1255180
- Report Number(s):
- LLNL-JRNL-663112
Journal ID: ISSN 0022-3263
- Grant/Contract Number:
- AC52-07NA27344; W911NF-07-0409
- Resource 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
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
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., 2015.
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. https://doi.org/10.1021/acs.joc.5b01493
Wang, Junpeng, Ong, Mitchell T., Kouznetsova, Tatiana B., Lenhardt, Jeremy M., Martínez, Todd J., and Craig, Stephen L. Mon .
"Catch and Release: Orbital Symmetry Guided Reaction Dynamics from a Freed “Tension Trapped Transition State”". United States. https://doi.org/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 = {Mon Aug 31 00:00:00 EDT 2015},
month = {Mon Aug 31 00:00:00 EDT 2015}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 15 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Chemiluminescence during the course of a reactive encounter; F+Na 2 →FNaNa ‡* →NaF+Na *
journal, December 1980
- Arrowsmith, P.; Bartoszek, F. E.; Bly, S. H. P.
- The Journal of Chemical Physics, Vol. 73, Issue 11
Chemiluminescent Reaction Channel Opened by Photon Absorption During Collision
journal, March 1980
- Hering, Peter; Brooks, Philip R.; Curl, R. F.
- Physical Review Letters, Vol. 44, Issue 10
Transition State Spectroscopy of Bimolecular Chemical Reactions
journal, October 1992
- Neumark, D. M.
- Annual Review of Physical Chemistry, Vol. 43, Issue 1
Transition-State Spectroscopy of Cyclooctatetraene
journal, June 1996
- Wenthold, P. G.; Hrovat, D. A.; Borden, W. T.
- Science, Vol. 272, Issue 5267
Stereochemistry of Electrocyclic Reactions
journal, January 1965
- Woodward, R. B.; Hoffmann, Roald
- Journal of the American Chemical Society, Vol. 87, Issue 2
Covalent Mechanochemistry: Theoretical Concepts and Computational Tools with Applications to Molecular Nanomechanics
journal, June 2012
- Ribas-Arino, Jordi; Marx, Dominik
- Chemical Reviews, Vol. 112, Issue 10
Mechanically-Induced Chemical Changes in Polymeric Materials
journal, November 2009
- Caruso, Mary M.; Davis, Douglas A.; Shen, Qilong
- Chemical Reviews, Vol. 109, Issue 11
Mechanochemistry: The Mechanical Activation of Covalent Bonds
journal, August 2005
- Beyer, Martin K.; Clausen-Schaumann, Hauke
- Chemical Reviews, Vol. 105, Issue 8
Mechanochemistry: One Bond at a Time
journal, June 2009
- Liang, Jian; Fernández, Julio M.
- ACS Nano, Vol. 3, Issue 7
Molecular Stress Relief through a Force-Induced Irreversible Extension in Polymer Contour Length
journal, November 2010
- Wu, Dong; Lenhardt, Jeremy M.; Black, Ashley L.
- Journal of the American Chemical Society, Vol. 132, Issue 45
Biasing reaction pathways with mechanical force
journal, March 2007
- Hickenboth, Charles R.; Moore, Jeffrey S.; White, Scott R.
- Nature, Vol. 446, Issue 7134
Force-induced activation of covalent bonds in mechanoresponsive polymeric materials
journal, May 2009
- Davis, Douglas A.; Hamilton, Andrew; Yang, Jinglei
- Nature, Vol. 459, Issue 7243
Adsorption-induced scission of carbon–carbon bonds
journal, March 2006
- Sheiko, Sergei S.; Sun, Frank C.; Randall, Adrian
- Nature, Vol. 440, Issue 7081
Trapping a Diradical Transition State by Mechanochemical Polymer Extension
journal, August 2010
- Lenhardt, J. M.; Ong, M. T.; Choe, R.
- Science, Vol. 329, Issue 5995
Tension Trapping of Carbonyl Ylides Facilitated by a Change in Polymer Backbone
journal, May 2012
- Klukovich, Hope M.; Kean, Zachary S.; Ramirez, Ashley L. Black
- Journal of the American Chemical Society, Vol. 134, Issue 23
Reactive Cross-Talk between Adjacent Tension-Trapped Transition States
journal, March 2011
- Lenhardt, Jeremy M.; Ogle, James W.; Ong, Mitchell T.
- Journal of the American Chemical Society, Vol. 133, Issue 10
Experimental Study of the Stereomutation of 1,1-Difluoro-2-ethyl-3-methylcyclopropane Confirms the Predicted Preference for Disrotatory Ring Opening and Closure
journal, June 1998
- Tian, Feng; Lewis, Scott B.; Bartberger, Michael D.
- Journal of the American Chemical Society, Vol. 120, Issue 24
Potential surfaces for cyclopropane stereomutations: what a difference geminal fluorines make
journal, January 1994
- Getty, Stephen J.; Hrovat, David A.; Xu, Jing Dong
- Journal of the Chemical Society, Faraday Transactions, Vol. 90, Issue 12
Ring-Opening Metathesis Polymerization of Functionalized Cyclooctenes by a Ruthenium-Based Metathesis Catalyst
journal, August 1995
- Hillmyer, Marc A.; Laredo, Walter R.; Grubbs, Robert H.
- Macromolecules, Vol. 28, Issue 18, p. 6311-6316
The mechanism of cavitation-induced polymer scission; experimental and computational verification
journal, September 2004
- Kuijpers, Martijn W. A.; Iedema, Piet D.; Kemmere, Maartje F.
- Polymer, Vol. 45, Issue 19
gem -Dichlorocyclopropanes as Abundant and Efficient Mechanophores in Polybutadiene Copolymers under Mechanical Stress
journal, August 2009
- Lenhardt, Jeremy M.; Black, Ashley L.; Craig, Stephen L.
- Journal of the American Chemical Society, Vol. 131, Issue 31
Inducing and quantifying forbidden reactivity with single-molecule polymer mechanochemistry
journal, February 2015
- Wang, Junpeng; Kouznetsova, Tatiana B.; Niu, Zhenbin
- Nature Chemistry, Vol. 7, Issue 4
First Principles Dynamics and Minimum Energy Pathways for Mechanochemical Ring Opening of Cyclobutene
journal, May 2009
- Ong, Mitchell T.; Leiding, Jeff; Tao, Hongli
- Journal of the American Chemical Society, Vol. 131, Issue 18
Bimodal Distribution of Lifetimes for an Intermediate from a Quasiclassical Dynamics Simulation
journal, January 1996
- Carpenter, Barry K.
- Journal of the American Chemical Society, Vol. 118, Issue 42
Investigation of Cyclopropane Stereomutation by Quasiclassical Trajectories on an Analytical Potential Energy Surface
journal, June 1997
- Hrovat, David A.; Fang, Shu; Borden, Weston Thatcher
- Journal of the American Chemical Society, Vol. 119, Issue 22
Activating catalysts with mechanical force
journal, April 2009
- Piermattei, Alessio; Karthikeyan, S.; Sijbesma, Rint P.
- Nature Chemistry, Vol. 1, Issue 2
Stress-Responsive Polymers Containing Cyclobutane Core Mechanophores: Reactivity and Mechanistic Insights
journal, August 2013
- Kean, Zachary S.; Niu, Zhenbin; Hewage, Gihan B.
- Journal of the American Chemical Society, Vol. 135, Issue 36
“Flex-Activated” Mechanophores: Using Polymer Mechanochemistry To Direct Bond Bending Activation
journal, May 2013
- Larsen, Michael B.; Boydston, Andrew J.
- Journal of the American Chemical Society, Vol. 135, Issue 22
Model studies of force-dependent kinetics of multi-barrier reactions
journal, September 2013
- Tian, Yancong; Kucharski, Timothy J.; Yang, Qing-Zheng
- Nature Communications, Vol. 4, Issue 1
A Remote Stereochemical Lever Arm Effect in Polymer Mechanochemistry
journal, October 2014
- Wang, Junpeng; Kouznetsova, Tatiana B.; Kean, Zachary S.
- Journal of the American Chemical Society, Vol. 136, Issue 43
NMR nomenclature. Nuclear spin properties and conventions for chemical shifts(IUPAC Recommendations 2001)
journal, January 2001
- Harris, Robin K.; Becker, Edwin D.; Cabral de Menezes, Sonia M.
- Pure and Applied Chemistry, Vol. 73, Issue 11
Mechanistic Studies on Zinc-Induced Addition of CF2Br2 to Olefins. A Novel Radical Reductive Cyclopropanation on the Zinc Surface
journal, February 1994
- Wu, Shi-Hui; Liu, Wei-Zhong; Jiang, Xi-Kui
- The Journal of Organic Chemistry, Vol. 59, Issue 4
The Complete Active Space Self-Consistent Field Method and its Applications in Electronic Structure Calculations
book, January 1987
- Roos, Björn O.
- Advances in Chemical Physics
Theoretical Studies of Electronically Excited States of Molecular Systems Using Multiconfigurational Perturbation Theory
journal, February 1999
- Roos, Björn O.
- Accounts of Chemical Research, Vol. 32, Issue 2
Works referencing / citing this record:
Force-Induced Catastrophes on Energy Landscapes: Mechanochemical Manipulation of Downhill and Uphill Bifurcations Explains the Ring-Opening Selectivity of Cyclopropanes
journal, February 2018
- Wollenhaupt, Miriam; Schran, Christoph; Krupička, Martin
- ChemPhysChem, Vol. 19, Issue 7
Steering chemical reactions with force
journal, November 2017
- Garcia-Manyes, Sergi; Beedle, Amy E. M.
- Nature Reviews Chemistry, Vol. 1, Issue 11