Understanding organic gas-phase anion molecule reactions

Although ionic reactions in the gas phase seem on the surface to be totally different from those in solution (e.g., they typically occur about 10(12) times more rapidly than their solution analogues and go about as fast at 10 K as they do at room temperature), they can, in fact, exhibit subtle steric, electronic, and isotopic effects. In this Perspective, we show how these differences arise, explain why gas-phase ion reactions can be both fast and selective, and discuss when they can and cannot be classified as ''hot'' reactions. We also give examples of the use of these reactions to devise new synthetic pathways, investigate reaction mechanisms, and generate important thermochemical data such as bond dissociation energies.