This laboratory has long been interested in the synthesis and structure of unusual molecules. These efforts have resulted in experimental realization of metalloaromaticity (the concept that metallic rings may also display traditional aromatic behavior) and novel compounds containing multiple bonding between main-group metals. Our recent efforts concerning the utilization of N-heterocyclic carbene ligands (L:) with main-group nonmetals such as boron, silicon, and phosphorus has resulted in carbene-stabilized examples of diborene,1,2 L:(H)B=B(H):L, disilicon,3 L:Si=Si:L, and diphosphorus,4 L:P- P:L. This presentation will highlight the interesting chemistry of these compounds and the critical role of the carbene ligand systems.