Force-Induced Catastrophes on Energy Landscapes: Mechanochemical Manipulation of Downhill and Uphill Bifurcations Explains the Ring-Opening Selectivity of Cyclopropanes

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F17%3A43917032" target="_blank" >RIV/60461373:22310/17:43917032 - isvavai.cz</a>

Result on the web

<a href="https://onlinelibrary.wiley.com/doi/full/10.1002/cphc.201701209" target="_blank" >https://onlinelibrary.wiley.com/doi/full/10.1002/cphc.201701209</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/cphc.201701209" target="_blank" >10.1002/cphc.201701209</a>

Result language

angličtina

Original language name

Force-Induced Catastrophes on Energy Landscapes: Mechanochemical Manipulation of Downhill and Uphill Bifurcations Explains the Ring-Opening Selectivity of Cyclopropanes

Original language description

The mechanochemistry of ring-opening reactions of cyclopropane derivatives turns out to be unexpectedly rich and puzzling. After showing that a rare so-called uphill bifurcation in the case of trans-gem-difluorocyclopropane turns into a downhill bifurcation upon substitution of fluorine by chlorine, bromine, and iodine in the thermal activation limit, the dichloro derivative is studied systematically in the realm of mechanochemical activation. Detailed exploration of the force-transformed potential energy surface of trans-gem-dichlorocyclopropane in terms of Dijkstra path analysis unveils a hitherto unknown topological catastrophe where the global shape of the energy landscape is fundamentally changed. From thermal activation up to moderately large forces, it is an uphill bifurcation that decides about dis- versus conrotatory ring-opening followed by separate transition states along both pathways. Above a critical force, the two distinct transition states merge to yield a single transition state such that the decision about the dis- versus conrotatory ring-opening process is taken at a newly established downhill bifurcation. The discovery of a force-induced qualitative change of the topology of a reaction network vastly transcends the previous understanding of the ring-opening reaction of this species. It would be astonishing to not discover a wealth of such catastrophes for mechanochemically activated reactions, which will greatly extend the known opportunities to manipulate chemical reaction networks.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

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OECD FORD branch

10403 - Physical chemistry

Project

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Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2017

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

ChemPhysChem

ISSN

1439-4235

e-ISSN

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Volume of the periodical

19

Issue of the periodical within the volume

7

Country of publishing house

DE - GERMANY

Number of pages

11

Pages from-to

837-847

UT code for WoS article

000429538400006

EID of the result in the Scopus database

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