Alkane complexes as intermediates in C-H bond activation reactions

The rearrangements of alkyl deuteride complexes are monitored and a kinetic model used to extract the rate constants for the fundamental processes involving the unseen alkane σ-complexes. Isotope effects for C-H and C-D bond formation and cleavage have been measured to permit these determinations. The relative rates of the processes available to an alkane σ-complex (C-H oxidative cleavage, C-D oxidative cleavage, dissociation, migration to an adjacent C-H bond) have been determined for methane, ethane, propane, butane, pentane, and hexane.