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The reaction of allyltriisopropylsilane with partially dehydroxylated sulfated zirconium oxide (SZO) forms surface organosilicon species. Solid‐state NMR studies of the organosilicon functionalizedSZOshows that electrophilic [TIPS][SZO] sites are present on the surface, in addition to less reactive TIPS‐O_xand SiO_xspecies. The electrophilic [TIPS][SZO] sites are strong Lewis acids from solid‐state³¹P NMR analysis of triethylphosphine oxide (O=PEt₃) contacted materials. [TIPS][SZO] is active in hydrodefluorination reactions in the presence of Et₃SiH.

 

The origin in deshielding of 29 Si NMR chemical shifts in R 3 Si–X, where X = H, OMe, Cl, OTf, [CH 6 B 11 X 6 ], toluene, and O X (O X = surface oxygen), as well as i Pr 3 Si + and Mes 3 Si + were studied using DFT methods. At the M06-L/6-31G(d,p) level of theory the geometry optimized structures agree well with those obtained experimentally. The trends in 29 Si NMR chemical shift also reproduce experimental trends; i Pr 3 Si–H has the most shielded 29 Si NMR chemical shift and free i Pr 3 Si + or isolable Mes 3 Si + have the most deshielded 29 Si NMR chemical shift. Natural localized molecular orbital (NLMO) analysis of the contributions to paramagnetic shielding ( σ p ) in these compounds shows that Si–R (R = alkyl, H) bonding orbitals are the major contributors to deshielding in this series. The Si–R bonding orbitals are coupled to the empty p-orbital in i Pr 3 Si + or Mes 3 Si + , or to the orbital in R 3 Si–X. This trend also applies to surface bound R 3 Si–O X . This model also explains chemical shift trends in recently isolated t Bu 2 SiH 2 + , t BuSiH 2 + , and SiH 3 + that show more shielded 29 Si NMR signals than R 3 Si + species. There is no correlation between isotropic 29 Si NMR chemical shift and charge at silicon. 

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(CF 3 ) 3 ) with silica partially dehydroxylated at 700 °C (SiO 2-700 ) 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 H 2 SO 4 , but higher than the strongest carborane acids, suggesting that deprotonated 1 would be a WCA. Reactions of 1 with NOct 3 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.