The synthesis of a series of isostructural organometallic complexes featuring Ae–Tr bonds (Ae = Be, Mg; Tr = Al, Ga, In) has been investigated, and their electronic structures probed by quantum chemical calculations. This systematic study allows for comparison, not only of the metal–metal bonding chemistries of the two lightest alkaline earth (Ae) elements, beryllium and magnesium, but also of the three triel (Tr) elements, aluminium, gallium, and indium. Computational analyses (NBO, QTAIM, EDA-NOCV) reveal that Be–Tr bonding is more covalent than Mg–Tr bonding. More strikingly, these calculations predict that the beryllium–indyl complex – featuring the first structurally characterised Be–In bond – should act as a source of nucleophilic beryllium. This has been confirmed experimentally by its reactivity towards methyl iodide, which yields the Be–Me functionality. By extension, the electrophilic character of the beryllium centre in the beryllium–gallyl complex contrasts with the umpoled, nucleophilic behaviour of the beryllium centre in both the -indyl and -aluminyl complexes.
