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. This minireview aims to comprehensively cover the current state of knowledge of tetryliumylidene ion [R-E:]+ (E = Si, Ge, Sn, Pb) chemistry regarding their syntheses, reactivity, and applications in transition metal-free catalytic reactions.