The transition metal mediated C-H activation and functionalisation of pyridines is a synthetic methodology of interest. In the last few years new strategies have emerged for the C-H activation of pyridines that are based on cooperative action of transition metal and main group elements contained within a single reactive species. Very recently, our group reported a well-defined Fe-Al complex that is capable of selectively breaking the sp C-H bond of pyridine (Figure ). Based on a combination of kinetics experiments and DFT calculations, we proposed that C -H bond activation occurred via a novel mechanism involving two consecutive elementary steps. In the first step, the C-H bond is broken through a reductive deprotonation by the Fe centre. In a second step, the deprotonated pyridyl group rearranges to form a strong Al-C bond, a process that drives the thermochemistry of the reaction. During our efforts to expand the scope of this reaction to substituted pyridines, we observed a series of unexpected results. Modification of the pyridine revealed a series of divergent pathways in which the proposed deprotonated intermediate can attack electrophilic or acidic sites of the β-diketiminate ligand. These unforeseen reactions provide additional experimental support for the proposed mechanism of C-H activation through reductive deprotonation and highlight the non-innocence of the β-diketiminate ligand in this system.