Divergent Fe-Mediated C–H Activation Paths Driven by Alkali Cations

The association of the ferrous complex FeIICl2(dmpe)2 (1) with alkali bases M(hmds) (M = Li, Na, K) proves to be an efficient platform for the activation of Ar–H bonds. Two mechanisms can be observed, leading to either Ar–FeII species by deprotonative ferration or hydrido species Ar–FeII–H by oxidative addition of transient Fe0(dmpe)2 generated by reduction of 1. Importantly, the nature of the alkali cation in M(hmds) has a strong influence on the preferred path. Starting from the same iron precursor, diverse catalytic applications can be explored by a simple modulation of the MI cation. Possible strategies enabling cross-coupling using arenes as pro-nucleophiles, reductive dehydrocoupling, or deuteration of B–H bonds are discussed.