This article highlights recent efforts of this laboratory in the stabilization of highly reactive, low-oxidation-state, main-group molecules using bulky N-heterocyclic carbene ligands [L: = :C{N(2,6-(Pr2C6H3)-C-i)CH}(2); L': = :C{N(2,4,6-Me3C6H2)CH}(2); L '': = :C{(i-Pr)NC(Me)}(2)]. The syntheses, structures, and computational studies of carbene-stabilized neutral diborenes [L:(H)B=B(H):L and L':(H)B=B(H):L'], a neutral Ga-6 octahedron (L '':Ga[Ga(4)Mes(4)]Ga:L ''), disilicon (L:Si=Si:L), bis-silylene [L:(Cl)Si-Si(Cl):L], dipnictogens (L:E-E:L, E = P, As; L':P-P:L'), and parent phosphinidene (L:PH) are discussed. Some of the unique challenges associated with this "carbene-stabilization" strategy are also presented.