Al(ORF)3 (RF = C(CF3)3) activated silica: a well-defined weakly coordinating surface anion. Issue 6 (2nd January 2020)

• Record Type: Journal Article
• Authors: Culver, Damien B.; Venkatesh, Amrit; Huynh, Winn; Rossini, Aaron J.; Conley, Matthew P.
• Is Part Of: Chemical science. Volume 11:Issue 6(2020)
• Page Start: 1510
• Page End: 1517
• Publication Date: 2020-01-02
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c9sc05904k
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : A strong Lewis acid coordinates to silanols on silica to form a strong acid, which acts as a weakly coordinating anion when deprotonated. Abstract : Weakly Coordinating Anions (WCAs) containing electron deficient delocalized anionic fragments that are reasonably inert allow for the isolation of strong electrophiles. Perfluorinated borates, perfluorinated aluminum alkoxides, and halogenated carborane anions are a few families of WCAs that are commonly used in synthesis. Application of similar design strategies to oxide surfaces is challenging. This paper describes the reaction of Al(OR F )3 *PhF (R F = C(CF3 )3 ) with silica partially dehydroxylated at 700 °C (SiO2-700 ) to form the bridging silanol Si–OH⋯Al(OR F )3 (1 ). DFT calculations using small clusters to model 1 show that the gas phase acidity (GPA) of the bridging silanol is 43.2 kcal mol −1 lower than the GPA of H2 SO4, but higher than the strongest carborane acids, suggesting that deprotonated 1 would be a WCA. Reactions of 1 with NOct3 show that 1 forms weaker ion-pairs than classical WCAs, but stronger ion-pairs than carborane or borate anions. Though 1 forms stronger ion-pairs than these state-of-the-art WCAs, 1 reacts with alkylsilanes to form silylium type surface species. To the best of our knowledge, this is the first example of a silylium supported on derivatized silica.