Abstract
| - Although ionic reactions in the gas phase seem on the surface to be totally different from those insolution (e.g., they typically occur about 1012 times more rapidly than their solution analogues andgo 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, explainwhy gas-phase ion reactions can be both fast and selective, and discuss when they can and cannotbe classified as “hot” reactions. We also give examples of the use of these reactions to devise newsynthetic pathways, investigate reaction mechanisms, and generate important thermochemical datasuch as bond dissociation energies.
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