To compare the ligand-based reduction chemistry of (EPh)(-) ligands in a metallocene environment to the sterically induced reduction chemistry of the (C5Me5)(-) ligands in (C5Me5)(3)SM, (C5Me5)(2)Sm(EPh) (E = S, Se, Te) complexes were synthesized and treated with substrates reduced by (C5Me5)(3)SM: cyclooctatetraene; azobenzene; phenazine. Reactions of PhEEPh with (C5Me5)(2)Sm(THF)(2) and (C5Me5)(2)SM produced THF-solvated monometallic complexes, (C5Me5)(2)SM(Ph)(THF), and their unsolvated dimeric analogues, [(C5Me5)(2)Sm(mu-EPh)](2), respectively. Both sets of the paramagnetic benzene chalcogenolate complexes were definitively identified by X-crystallography and form homologous series. Only the (TePh)(-) complexes show reduction reactivity and only upon heating to 65 degrees C.