10.1021/jacs.7b11334.s003 William Cullen William Cullen Alexander J. Metherell Alexander J. Metherell Ashley B. Wragg Ashley B. Wragg Christopher G. P. Taylor Christopher G. P. Taylor Nicholas H. Williams Nicholas H. Williams Michael D. Ward Michael D. Ward Catalysis in a Cationic Coordination Cage Using a Cavity-Bound Guest and Surface-Bound Anions: Inhibition, Activation, and Autocatalysis American Chemical Society 2018 Cationic Coordination Cage Kemp elimination anion hydroxide cage surface product 2- cyanophenolate cavity-bound guest 2- cyanophenolate M 8 L 12 coordination cage cationic cage surface sigmoidal reaction profile autocatalytic pathway default reaction pathway 2018-02-07 00:00:00 Dataset https://acs.figshare.com/articles/dataset/Catalysis_in_a_Cationic_Coordination_Cage_Using_a_Cavity-Bound_Guest_and_Surface-Bound_Anions_Inhibition_Activation_and_Autocatalysis/5891998 The Kemp elimination (reaction of benz­isox­azole with base to give 2-cyanophenolate) is catalyzed in the cavity of a cubic M<sub>8</sub>L<sub>12</sub> coordination cage because of a combination of (i) benz­isox­azole binding in the cage cavity driven by the hydrophobic effect, and (ii) accumulation of hydroxide ions around the 16+ cage surface driven by ion-pairing. Here we show how reaction of the cavity-bound guest is modified by the presence of other anions which can also accumulate around the cage surface and displace hydroxide, inhibiting catalysis of the cage-based reaction. Addition of chloride or fluoride inhibits the reaction with hydroxide to the extent that a new autocatalytic pathway becomes apparent, resulting in a sigmoidal reaction profile. In this pathway the product 2-cyanophenolate itself accumulates around the cationic cage surface, acting as the base for the next reaction cycle. The affinity of different anions for the cage surface is therefore 2-cyanophenolate (generating autocatalysis) > chloride > fluoride (which both inhibit the reaction with hydroxide but cannot deprotonate the benz­isox­azole guest) > hydroxide (default reaction pathway). The presence of this autocatalytic pathway demonstrates that a reaction of a cavity-bound guest can be induced with different anions around the cage surface in a controllable way; this was confirmed by adding different phenolates to the reaction, which accelerate the Kemp elimination to different extents depending on their basicity. This represents a significant step toward the goal of using the cage as a catalyst for bimolecular reactions between a cavity-bound guest and anions accumulated around the surface.