In summary, the reaction of a Fe-Al complex with several substituted pyridines has been reported. A series of divergent pathways have been identified that result in (i) C-Al bond formation, (ii) C-C bond formation, and (iii) ligand deprotonation. Common to these pathways is the formation of an anionic intermediate generated by site-selective deprotonation of either sp 2 or sp 3 positions of the pyridine substrate. The data provide additional support for a novel mechanism of C-H activation by heterometallic complexes previously reported by our group, they also highlight the potential non-innocence of the β-diketiminate ligand in these systems.