Bambusurils as a mechanistic tool for probing anion effects

J 2019

Bambusurils as a mechanistic tool for probing anion effects

JASÍKOVÁ, Lucie; Maitê RODRIGUES; Jana LAPEŠOVÁ; Tomáš LÍZAL; Vladimír ŠINDELÁŘ et al.

Základní údaje

Originální název

Bambusurils as a mechanistic tool for probing anion effects

Autoři

JASÍKOVÁ, Lucie; Maitê RODRIGUES; Jana LAPEŠOVÁ; Tomáš LÍZAL; Vladimír ŠINDELÁŘ a Jana ROITHOVÁ

Vydání

FARADAY DISCUSSIONS, CAMBRIDGE, ROYAL SOC CHEMISTRY, 2019, 1359-6640

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10403 Physical chemistry

Stát vydavatele

Velká Británie a Severní Irsko

Utajení

není předmětem státního či obchodního tajemství

Odkazy

Full Text

Impakt faktor

Impact factor: 3.797

Označené pro přenos do RIV

Ano

Kód RIV

RIV/00216224:14310/19:00110762

Organizační jednotka

Přírodovědecká fakulta

Klíčová slova anglicky

N-HETEROCYCLIC CARBENES; GOLD(I)-CATALYZED HYDROALKOXYLATION; MASS-SPECTROMETRY; COUNTERION; ALKOXYLATION; ALKYNES; HYDROPHENOXYLATION; HYDROGENATION; CATALYSIS; COMPLEXES

Štítky

rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 17. 2. 2023 21:45, Mgr. Michaela Hylsová, Ph.D.

Anotace

V originále

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.

Návaznosti

EF16_013/0001761, projekt VaV

Název: RECETOX RI

LM2015051, projekt VaV

Název: Centrum pro výzkum toxických látek v prostředí (Akronym: RECETOX RI)

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, Výzkumná infrastruktura RECETOX

Citovat

JASÍKOVÁ, Lucie; Maitê RODRIGUES; Jana LAPEŠOVÁ; Tomáš LÍZAL; Vladimír ŠINDELÁŘ a Jana ROITHOVÁ. Bambusurils as a mechanistic tool for probing anion effects. FARADAY DISCUSSIONS. CAMBRIDGE: ROYAL SOC CHEMISTRY, 2019, roč. 220, DEC, s. 58-70. ISSN 1359-6640. Dostupné z: https://doi.org/10.1039/C9FD00038K.

@article{1561376,
   author = {Jasíková, Lucie and Rodrigues, Maitê and Lapešová, Jana and Lízal, Tomáš and Šindelář, Vladimír and Roithová, Jana},
   article_location = {CAMBRIDGE},
   article_number = {DEC},
   doi = {https://doi.org/10.1039/C9FD00038K},
   keywords = {N-HETEROCYCLIC CARBENES; GOLD(I)-CATALYZED HYDROALKOXYLATION; MASS-SPECTROMETRY; COUNTERION; ALKOXYLATION; ALKYNES; HYDROPHENOXYLATION; HYDROGENATION; CATALYSIS; COMPLEXES},
   language = {eng},
   issn = {1359-6640},
   journal = {FARADAY DISCUSSIONS},
   title = {Bambusurils as a mechanistic tool for probing anion effects},
   url = {https://pubs.rsc.org/en/content/articlelanding/2019/FD/C9FD00038K#!divAbstract},
   volume = {220},
   year = {2019}
}

TY  - JOUR
ID  - 1561376
AU  - Jasíková, Lucie - Rodrigues, Maitê - Lapešová, Jana - Lízal, Tomáš - Šindelář, Vladimír - Roithová, Jana
PY  - 2019
TI  - Bambusurils as a mechanistic tool for probing anion effects
JF  - FARADAY DISCUSSIONS
VL  - 220
IS  - DEC
SP  - 58-70
EP  - 58-70
PB  - ROYAL SOC CHEMISTRY
SN  - 13596640
KW  - N-HETEROCYCLIC CARBENES
KW  - GOLD(I)-CATALYZED HYDROALKOXYLATION
KW  - MASS-SPECTROMETRY
KW  - COUNTERION
KW  - ALKOXYLATION
KW  - ALKYNES
KW  - HYDROPHENOXYLATION
KW  - HYDROGENATION
KW  - CATALYSIS
KW  - COMPLEXES
UR  - https://pubs.rsc.org/en/content/articlelanding/2019/FD/C9FD00038K#!divAbstract
L2  - https://pubs.rsc.org/en/content/articlelanding/2019/FD/C9FD00038K#!divAbstract
N2  - 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.
ER  -

JASÍKOVÁ, Lucie; Maitê RODRIGUES; Jana LAPEŠOVÁ; Tomáš LÍZAL; Vladimír ŠINDELÁŘ a Jana ROITHOVÁ. Bambusurils as a mechanistic tool for probing anion effects. \textit{FARADAY DISCUSSIONS}. CAMBRIDGE: ROYAL SOC CHEMISTRY, 2019, roč.~220, DEC, s.~58-70. ISSN~1359-6640. Dostupné z: https://doi.org/10.1039/C9FD00038K.

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