JASÍKOVÁ, Lucie, Maitê RODRIGUES, Jana LAPEŠOVÁ, Tomáš LÍZAL, Vladimír ŠINDELÁŘ and Jana ROITHOVÁ. Bambusurils as a mechanistic tool for probing anion effects. FARADAY DISCUSSIONS. CAMBRIDGE: ROYAL SOC CHEMISTRY, 2019, vol. 220, DEC, p. 58-70. ISSN 1359-6640. Available from: https://dx.doi.org/10.1039/C9FD00038K. |
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@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 = {http://dx.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 and Jana ROITHOVÁ. Bambusurils as a mechanistic tool for probing anion effects. \textit{FARADAY DISCUSSIONS}. CAMBRIDGE: ROYAL SOC CHEMISTRY, 2019, vol.~220, DEC, p.~58-70. ISSN~1359-6640. Available from: https://dx.doi.org/10.1039/C9FD00038K.
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