Understanding and Predicting Post H‑Atom Abstraction Selectivitythrough Reactive Mode Composition Factor Analysis
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F20%3A00522642" target="_blank" >RIV/61388955:_____/20:00522642 - isvavai.cz</a>
Result on the web
<a href="http://hdl.handle.net/11104/0307104" target="_blank" >http://hdl.handle.net/11104/0307104</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/jacs.9b12800" target="_blank" >10.1021/jacs.9b12800</a>
Alternative languages
Result language
angličtina
Original language name
Understanding and Predicting Post H‑Atom Abstraction Selectivitythrough Reactive Mode Composition Factor Analysis
Original language description
The selective functionalization of C–H bonds is one of the Grails of synthetic chemistry. In this work, we demonstrate that the selectivity toward fast hydroxylation or radical diffusion (known as the OH-rebound and dissociation mechanisms) following H-atom abstraction (HAA) from a substrate C–H bond by high-valent iron-oxo oxidants is already encoded in the HAA step when the post-HAA barriers are much lower than the preceding one. By applying the reactive mode composition factor (RMCF) analysis, which quantifies the kinetic energy distribution (KED) at the reactive mode (RM) of transition states, we show that reactions following the OH-rebound coordinate concentrate the RM kinetic energy on the motion of the reacting oxygen atom and the nascent substrate radical, whereas reactions following the dissociation channel localize most of their kinetic energy in H-atom motion. These motion signatures serve to predict the post-HAA selectivity, and since KED is affected by the free energy of reaction and asynchronicity (factor η) of HAA, we show that bimolecular HAA reactions in solution that are electron transfer-driven and highly exergonic have the lowest fraction of KED on the transferred H-atom and the highest chance to follow rebound hydroxylation. Finally, the RMCF analysis predicts that the H/D primary kinetic isotope effect can serve as a probe for these mechanisms, as confirmed in virtually all reported examples in the literature.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - 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
Result continuities
Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2020
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of the American Chemical Society
ISSN
0002-7863
e-ISSN
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Volume of the periodical
142
Issue of the periodical within the volume
8
Country of publishing house
US - UNITED STATES
Number of pages
12
Pages from-to
3947-3958
UT code for WoS article
000517360400033
EID of the result in the Scopus database
2-s2.0-85080983854