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          Institute: MPI für bioanorganische Chemie     Collection: MPI für bioanorganische Chemie     Display Documents



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ID: 712892.0, MPI für bioanorganische Chemie / MPI für bioanorganische Chemie
Disfavoring Mechanochemical Reactions by Stress-Induced Steric Hindrance
Authors:Krupicka, Martin; Marx, Dominik
Language:English
Date of Publication (YYYY-MM-DD):2015
Title of Journal:Journal of Chemical Theory and Computation
Journal Abbrev.:J.Chem.Theory Comput.
Volume:11
Issue / Number:3
Start Page:841
End Page:846
Review Status:Internal review
Audience:Experts Only
Abstract / Description:Mechanochemical activation of covalent bonds using sonication, force spectroscopy, or molecular force probes usually lowers activation energies and thus accelerates reactions. However, applying mechanical forces to complex molecules is known to not only stretch covalent bonds but also to distort the molecular skeleton that hosts the activated bonds-leading to nonmonotonous behavior as a function of force. Here, the Bell-Taft model is introduced and validated which both rationalizes and quantifies such nonlinear effects on activation energies, including the transition from catch bonds at low forces to slip binding, in terms of steric hindrance caused by force-induced conformational distortions. The fully parametrized version of the model relies exclusively on readily accessible zero-force data and thus allows one to qualitatively explore mechanically induced reactivity changes in complex setups.
Comment of the Author/Creator:Date: 2015, MAR 2015
External Publication Status:published
Document Type:Article
Communicated by:N. N.
Affiliations:MPI für bioanorganische Chemie
Identifiers:ISI:000350918300001 [ID No:1]
ISSN:1549-9618 [ID No:2]
DOI:10.1021/ct501058a [ID No:3]
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