H-transfer rates in ion-neutral complexes versus those in intact aliphatic ions

Abstract

The relative rates of H‐transfer between partners in ion–neutral complexes were compared with those in intramolecular rearrangements using results of first differential photoionization mass spectrometry measurements. Complex‐mediated H‐transfers are inferred to have rates of the same order as those for intramolecular hydrogen rearrangements, suggesting a similar range of motion of the reactive sites in both types of reactions. It is also concluded that at their fastest H‐transfers take place between the partners in ion–neutral complexes within at most the time of several rotations of the partners in the complexes. Copyright © 1999 John Wiley & Sons, Ltd.