Several 19-electron sandwich compounds are known to exist as “2×18-electron” dimers. Recently it has been shown that, despite their air stability in the solid state, some of these dimers act as powerful reductants when co-deposited from either the gas phase or from solution and that this behavior can be useful in n-doping materials for organic electronics, including compounds with moderate electron affinities, such as 6,13-bis[tri(isopropyl)silylethynyl]pentacene (3). This paper addresses the mechanisms by which the dimers of 1,2,3,4,5-pentamethylrhodocene (1 b2), (pentamethylcyclopentadienyl)(1,3,5-trialkylbenzene)ruthenium (alkyl=Me, 2 a2; alkyl=Et, 2 b2), and (pentamethylcyclopentadienyl)(benzene)iron (2 c2) react with 3 in solution. Vis/NIR and NMR spectroscopy, and X-ray crystallography indicate that the products of these solution reactions are 3.− salts of the monomeric sandwich cations. Vis/NIR kinetic studies for the Group 8 dimers are consistent with a mechanism whereby an endergonic electron transfer from the dimer to 3 is followed by rapid cleavage of the dimer cation. NMR crossover experiments with partially deuterated derivatives suggest that the CC bond in the 1 b2 dimer is much more readily broken than that in 2 a2; consistent with this observation, Vis/NIR kinetic measurements suggest that the solution reduction of 3 by 1 b2 can occur by both the mechanism established for the Group 8 species and by a mechanism in which an endergonic dissociation of the dimer is followed by rapid electron transfer from monomeric 1 b to 3.