Tetryliumylidene ions in synthesis and catalysis

Tetryliumylidene ions ([R-E:]⁺), recognised for their intriguing electronic properties, have attracted considerable interest. These positively charged species, with two vacant p-orbitals and a lone pair at the E(ii) centre (E = Si, Ge, Sn, Pb), can be viewed as the combination of tetrylenes (R₂E:) and tetrylium ions ([R₃E]⁺), which makes them potent Lewis ambiphiles. Such electronic features highlight the potential of tetryliumylidenes for single-site small molecule activation and transition metal-free catalysis. The effective utilisation of the electrophilicity and nucleophilicity of tetryliumylidenes is expected to stem from appropriate ligand choice. For most of the isolated tetryliumylidenes, electron donor- and/or kinetic stabilisation is necessary. This minireview highlights the developments in tetryliumylidene syntheses and the progress of research towards their reactivity and applications in catalytic reactions.