Quantifiable polarity match effect on C–H bond cleavage reactivity and its limits in reaction design

Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F23%3A00567641" target="_blank" >RIV/61388955:_____/23:00567641 - isvavai.cz</a>
Result on the web
<a href="https://hdl.handle.net/11104/0338871" target="_blank" >https://hdl.handle.net/11104/0338871</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/D2DT04018B" target="_blank" >10.1039/D2DT04018B</a>

Result language
angličtina
Original language name
Quantifiable polarity match effect on C–H bond cleavage reactivity and its limits in reaction design
Original language description
When oxidants favour cleaving a strong C−H bond at the expense of weaker ones, which are otherwise inherently preferred due to their favourable reaction energy, reactivity factors such as the polarity match effect are often invoked. Polarity match follows the intuition of electrophilic (nucleophilic) oxidants reacting faster with nucleophilic (electrophilic) C−H bonds. Nevertheless, this concept is purely qualitative and is best suited for a posteriori rationalization of experimental observations. Here, we propose and inspect two methods to quantify polar effects in C−H cleavage reactions, one by computation via the difference of atomic charges (Δq) of reacting atoms, and one amenable to experimental measurement through asynchronicity factors, η. By their application to three case studies, we observe that both Δq and η faithfully capture the notion of polarity match. The polarity match model, however, proves insufficient as a predictor of H-atom abstraction reactivity and we discourage its use as a standalone variable in reaction design. Besides this caveat, η and Δq (through its mapping on η) allow the implementation of polarity match into a Marcus-type model of reactivity, alleviating its shortcomings and making reaction planning feasible.n
Czech name
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Czech description
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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

Project
<a href="/en/project/GA21-10383S" target="_blank" >GA21-10383S: Control of Reaction Selectivity by Asynchronicity</a><br>
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year
2023
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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