Bambusurils as a mechanistic tool for probing anion effects

Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00020711%3A_____%2F19%3A00004907" target="_blank" >RIV/00020711:_____/19:00004907 - isvavai.cz</a>
Alternative codes found
RIV/00216224:14310/19:00110762 RIV/00216208:11310/19:10408845
Result on the web
<a href="http://dx.doi.org/10.1039/c9fd00038k" target="_blank" >http://dx.doi.org/10.1039/c9fd00038k</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/c9fd00038k" target="_blank" >10.1039/c9fd00038k</a>

Result language
angličtina
Original language name
Bambusurils as a mechanistic tool for probing anion effects
Original language description
Bambusuril macrocycles have high affinity towards anions (X-) such as PF6- and SbF6- or BF4- and ClO4-. Therefore, addition of bambusurils to reaction mixtures containing these anions effectively removes the free anions from the reaction process. Hence, comparing reactions with and without addition of bambusurils can demonstrate whether the anions actively participate in the reaction mechanism or not. We show this approach for gold(i) mediated addition of methanol to an alkyne. The reaction mechanism can proceed via monoaurated intermediates (e.g., in catalysis with [(IPr)AuX]) or via diaurated intermediates (e.g., in catalysis with [(PPh3)AuX]). We show that anions X- slightly affect the reaction rates, however the effect stays almost the same even after their encapsulation in the cavity of bambusurils. We also demonstrate that X- affects the overall reaction rate in the very same way as the reaction rate of the protodeauration step. All results are consistent with the indirect effect of X- by the acidity of the conjugated acid HX on the rate-determining step. There is no evidence that a direct involvement of X- would affect the reaction rate.
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
10400 - Chemical sciences

Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
V - Vyzkumna aktivita podporovana z jinych verejnych zdroju

Publication year
2019
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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