Solution-based n-doping of the polymer poly{[N,N′-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)} [P(NDI2OD-T2)] and the small molecule 6,13-bis(tri(isopropyl)silylethynyl)pentacene (TIPS-pentacene) is realized with the air-stable dimers of rhodocene, [RhCp2]2, and ruthenium(pentamethylcyclopentdienyl)(1,3,5-triethylbenzene), [Cp*Ru(TEB)]2. Fermi level shifts, measured by direct and inverse photoemission spectroscopy, and orders of magnitude increase in current density and film conductivity point to strong n-doping in both materials. The strong reducing power of these air-stable dopants is demonstrated through the n-doping of TIPS-pentacene, a material with low electron affinity (3.0 eV). Doping-induced reduction of the hopping transport activation energy indicates that the increase in film conductivity is due in part to the filling of deep gap states by carriers released by the dopants.