Thermal reactions of proton-bound dimers, (CH3CN)2H (+), (CH3OCH3)2H (+), and (CH3COCH3)2H(+), were studied using a selected ion flow tube. Reactions observed include association, switching, and proton transfer. The association channel was observed only for base molecules that had hydrogen bonding protons such as NH3, CH3NH2, (CH3)2NH, and CH3OH. An association-insertion mechaniSoc was proposed in which the central proton of the symmetrically bound dimers is replaced by a protonated base, for example, NH 4 (+) . These reactions are relatively slow, which demonstrates a central barrier along the potential energy surface. Ether-containing dimers do not demonstrate this insertion reaction, except for diethers, for example, CH3OCH2CH2OCH3, which can form stable bicyclic structures. Dimers such as (HCOOH)2H(+), which possess hydrogen bonding protons in the periphery, undergo switching reactions with ammonia and no insertion.