In summary, we report an unusual ligand migration event at an Fe-Al heterometallic complex. This event involves the apparent initial coordination of an exogenous ligand (e.g. CO or CNR) to Al followed by migration to the Fe site which occurs with concurrent migration of a hydride ligand from Fe to Al. The overall process can be conceptualised as a dyotropic rearrangement. DFT calculations are consistent with the characterisation of this reaction as 1,2-dyotropic shift, a rare and understudied process in heterobimetallic systems. This process appears to have some important differences to type I dyotropic rearrangement observed in organic compounds. Detailed computational analysis indicates a stepwise mechanism that involves a bridged intermediate, which is a precursor to a dyotropic transition state. Calculations indicate that the metal-metal bond in the bimetallic core breaks and the re-forms across the reaction coordinate, suggesting it responds to changes in electronic structure brought on by the migration of the ligands between the two metals. The 1,2-dyotropic shift fundamentally alters the structure of the heterometallic, exposing new types of reactivity. Specifically, migration of hydride from Fe to a terminal position on Al greatly increases its nucleophilicity and facilitates onwards reactions not observed prior to the dyotropic shift. The enhanced reactivity was demonstrated by insertion reactions with CO2, tert-butyl isocyanate and isocyanides. Our results shed new light on types of ligand exchange processes possible in heterometallic complexes. These events are not only mechanistically divergent from established monometallic complexes and analogous organics systems, but also fundamentally change the properties and reactivity of heterometallic complexes. Our findings might stimulate improved understanding of reactivity patterns in heterometallic complexes of catalytic processes where metal-metal cooperativity is key to successful turnover.