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Al(OC(CF ) )(PhF) reacts with silanols present on partially dehydroxylated silica to form well-defined ≡SiOAl(OC(CF ) ) (O(Si≡) ) (1). Al NMR and DFT calculations with a small cluster model to approximate the silica surface show that the aluminum in 1 adopts a distorted trigonal bipyramidal coordination geometry by coordinating to a nearby siloxane bridge and a fluorine from the alkoxide. Fluoride ion affinity (FIA) calculations follow experimental trends and show that 1 is a stronger Lewis acid than B(C F ) and Al(OC(CF ) )(PhF) but is weaker than Al(OC(CF ) ) and Pr Si . Cp Zr(CH ) reacts with 1 to form [Cp ZrCH ][≡SiOAl(OC(CF ) ) (CH )] (3) by methide abstraction. This reactivity pattern is similar to reactions of organometallics with the proposed strong Lewis acid sites present on Al O .
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