On the mechanism of Gif reactions

Gif chemistry converts saturated hydrocarbons selectively into ketones. On a limited conversion of up to about 25%, the yield is quantitative. Two manifolds can be distinguished: Fe-III-Fe-V and Fe-II-Fe-IV. The first manifold, with a few exceptions, does not involve radical chemistry. The second always affords carbon radicals. However, for both manifolds, the K.I.E. is identical at about 2.1 and the selectivity for secondary positions is the same. The activation process, in both cases, requires the presence of an appropriate carboxylate ligand and affords a species which reacts faster with saturated hydrocarbons than with substrates which are traditionally more easily oxidized.