Emerging Chemistry of Main Group Element-Based Dithiolene Complexes

While transition metals have played a dominant role in the development of dithiolene chemistry, their main-group element-based counterparts have received considerably less attention. This laboratory recently reported the first structurally characterized lithium dithiolene radical, via reaction of the anionic N-heterocyclic dicarbene with elemental sulfur. This radical provides an effective synthetic platform to access the largely unexplored main group element-based dithiolene chemistry. This presentation will primarily focus on our latest progress in this research area, including the synthesis and characterization of a magnesium(II) dithiolene monoradical, an aluminum(III) tris(dithiolene) triradical, germanium(II) and germanium(IV) dithiolene complexes, and Lewis base-stabilized dithiolene zwitterions. Moreover, the utility of the CAAC-dithiolene zwitterion (CAAC = cyclic(alkyl)(amino)carbene) in small molecule activation and the unusual nucleophilic reactivity of the dithiolene-based N-heterocyclic silane will also be addressed.