Flyby reaction trajectories: Chemical dynamics under extrinsic force
Abstract
Dynamic effects are an important determinant of chemical reactivity and selectivity, but the deliberate manipulation of atomic motions during a chemical transformation is not straightforward. In this work, we demonstrate that extrinsic force exerted upon cyclobutanes by stretching pendant polymer chains influences product selectivity through force-imparted nonstatistical dynamic effects on the stepwise ring-opening reaction. The high product stereoselectivity is quantified by carbon-13 labeling and shown to depend on external force, reactant stereochemistry, and intermediate stability. Computational modeling and simulations show that, besides altering energy barriers, the mechanical force activates reactive intramolecular motions nonstatistically, setting up “flyby trajectories” that advance directly to product without isomerization excursions. A mechanistic model incorporating nonstatistical dynamic effects accounts for isomer-dependent mechanochemical stereoselectivity.
- Authors:
-
[1];
[2];
[2];
[1];
[1];
[1];
[2];
[1]
- Univ. of Illinois at Urbana-Champaign, IL (United States)
- Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); German Research Foundation (DFG); US Army Research Office (ARO)
- OSTI Identifier:
- 1820150
- Grant/Contract Number:
- AC02-76SF00515; CMMI-19-33932; W911NF-15-1-0525; 419817859
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Science
- Additional Journal Information:
- Journal Volume: 373; Journal Issue: 6551; Journal ID: ISSN 0036-8075
- Publisher:
- AAAS
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Liu, Yun, Holm, Soren, Meisner, Jan, Jia, Yuan, Wu, Qiong, Woods, Toby J., Martinez, Todd J., and Moore, Jeffrey S. Flyby reaction trajectories: Chemical dynamics under extrinsic force. United States: N. p., 2021.
Web. doi:10.1126/science.abi7609.
Liu, Yun, Holm, Soren, Meisner, Jan, Jia, Yuan, Wu, Qiong, Woods, Toby J., Martinez, Todd J., & Moore, Jeffrey S. Flyby reaction trajectories: Chemical dynamics under extrinsic force. United States. https://doi.org/10.1126/science.abi7609
Liu, Yun, Holm, Soren, Meisner, Jan, Jia, Yuan, Wu, Qiong, Woods, Toby J., Martinez, Todd J., and Moore, Jeffrey S. Fri .
"Flyby reaction trajectories: Chemical dynamics under extrinsic force". United States. https://doi.org/10.1126/science.abi7609. https://www.osti.gov/servlets/purl/1820150.
@article{osti_1820150,
title = {Flyby reaction trajectories: Chemical dynamics under extrinsic force},
author = {Liu, Yun and Holm, Soren and Meisner, Jan and Jia, Yuan and Wu, Qiong and Woods, Toby J. and Martinez, Todd J. and Moore, Jeffrey S.},
abstractNote = {Dynamic effects are an important determinant of chemical reactivity and selectivity, but the deliberate manipulation of atomic motions during a chemical transformation is not straightforward. In this work, we demonstrate that extrinsic force exerted upon cyclobutanes by stretching pendant polymer chains influences product selectivity through force-imparted nonstatistical dynamic effects on the stepwise ring-opening reaction. The high product stereoselectivity is quantified by carbon-13 labeling and shown to depend on external force, reactant stereochemistry, and intermediate stability. Computational modeling and simulations show that, besides altering energy barriers, the mechanical force activates reactive intramolecular motions nonstatistically, setting up “flyby trajectories” that advance directly to product without isomerization excursions. A mechanistic model incorporating nonstatistical dynamic effects accounts for isomer-dependent mechanochemical stereoselectivity.},
doi = {10.1126/science.abi7609},
journal = {Science},
number = 6551,
volume = 373,
place = {United States},
year = {Fri Jul 09 00:00:00 EDT 2021},
month = {Fri Jul 09 00:00:00 EDT 2021}
}
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