The tension-activated carbon–carbon bond
Name
Sun_Chem_2024.pdf
Description
Accepted version
Size
312.12 KB
Format
Adobe PDF
Checksum (MD5)
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Author(s)
Sun, Yunyan
Kevlishvili, Ilia
Kouznetsova, Tatiana B
Burke, Zach P
Craig, Stephen L
Kulik, Heather J
Moore, Jeffrey S
Date Issued
October 10, 2024
Journal
Chem
Publisher
Elsevier BV
Citation
Sun, Yunyan, Kevlishvili, Ilia, Kouznetsova, Tatiana B, Burke, Zach P, Craig, Stephen L et al. 2024. "The tension-activated carbon–carbon bond." Chem, 10 (10).
Version
Author's final manuscript
Abstract
Mechanical force drives distinct chemical reactions; yet, its vectoral nature results in complicated coupling with reaction trajectories. Here, we utilize a physical organic model inspired by the classical Morse potential and its differential forms to identify effective force constant (k eff) and reaction energy (ΔE) as key molecular features that govern mechanochemical kinetics. Through a comprehensive experimental and computational investigation with four norborn-2-en-7-one (NEO) mechanophores, we establish the relationship between these features and the force-dependent energetic changes along the reaction pathways. We show that the complex kinetic behavior of the tensioned bonds is generally and quantitatively predicted by a simple multivariate linear regression based on the two easily computed features with a straightforward workflow. These results demonstrate a general mechanistic framework for mechanochemical reactions under tensile force and provide a highly accessible tool for the large-scale computational screening in the design of mechanophores.
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
Massachusetts Institute of Technology. Department of Chemistry
Terms of Use
Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
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DOI of Published Version
10.1016/j.chempr.2024.05.012
