The stepwise binding energies (¢H°n-1,n) of 1-8 water molecules to benzene¥+ [Bz¥+(H2O)n] were determined by equilibrium measurements using an ion mobility cell. The stepwise hydration energies, ¢H°n-1,n, are nearly constant at 8.5 ( 1 kcal mol-1 from n ) 1-6. Calculations show that in the n ) 1-4 clusters, the benzene¥+ ion retains over 90% of the charge, and it is externally solvated, that is, hydrogen bonded to an (H2O)n cluster. The binding energies and entropies are larger in the n ) 7 and 8 clusters, suggesting cyclic or cage-like water structures. The concentration of the n ) 3 cluster is always small, suggesting that deprotonation depletes this ion, consistent with the thermochemistry since associative deprotonation Bz¥+(H2O)n-1 + H2O f C6H5 ¥ + (H2O)nH+ is thermoneutral or exothermic for n g 4. Associative intracluster proton transfer Bz¥+(H2O)n-1 + H2O f C6H5 ¥(H2O)nH+ would be also exothermic for n g 4, but lack of H/D exchange with D2O shows that the proton remains on C6H6¥+ in the observed Bz¥+(H2O)n clusters. This suggests a barrier to intracluster proton transfer, and as a result, the [Bz¥+(H2O)n]* activated complexes either undergo dissociative proton transfer, resulting in deprotonation and generation of (H2O)nH+, or become stabilized. The rate constant for the deprotonation reaction shows a uniquely large negative temperature coefficient of k ) cT-67(4 (or activation energy of -34 ( 1 kcal mol-1), caused by a multibody mechanism in which five or more components need to be assembled for the reaction.