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

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.