This laboratory has long pursued the synthesis, structure, and reactivity of unusual molecules that prominently feature main group elements. These efforts resulted in several significant milestones including the experimental realization of “metalloaromaticity" (the concept that metallic rings may also display traditional aromatic behavior as exhibited by benzene), synthesis of the first molecule containing a boron-boron double bond—the first “diborene”, and synthesis of the first molecule containing a triple bond between two main group metals (the gallium analog of acetylene). Research efforts have also concerned carbene stabilization of highly reactive main group molecules such diphosphorus (P2), diarsenic (As2), and disilicon (Si2). This presentation will prominently highlight our efforts to synthetically augment the molecular template of N-heterocyclic carbenes and their surprising conversion to stable dithiolene-based chemical radicals, which have shown promise in the activation of small molecules, such as ammonia.