This report describes routes to iron dithiolato carbonyls that do not require preformed iron carbonyls. The reaction of FeCl2, Zn, and Q(2)S(2)C(n)H(2n) (Q(+) = Na+, Et3NH+) under an atmosphere of CO affords Fe-2(S2CnH2n)(CO)(6) (n = 2, 3) in yields >70%. The method was employed to prepare Fe-2(S2C2H4)((CO)-C-13)(6). Treatment of these carbonylated mixtures with tertiary phosphines, instead of Zn, gave the ferrous species Fe-3(S2C3H6)(3)(CO)(4)(PR3)(2), for R = Et, Bu, and Ph. Like the related complex Fe-3(SPh)(6)(CO)(6), these compounds consist of a linear arrangement of three conjoined face-shared octahedral centers. Omitting the phosphine but with an excess of dithiolate, we obtained the related mixed-valence triiron species [Fe-3(S2CnH2n)(4)(CO)(4)](-). The highly reducing all-ferrous species [Fe-3(S2CnH2n)4(CO)4](2-) is implicated as an intermediate in this transformation. Reactive forms of iron, prepared by the method of Rieke, also combined with dithiols under a CO atmosphere to give Fe-2(S2CnH2n)(CO)(6) in modest yields under mild conditions. Studies on the order of addition indicate that ferrous thiolates are formed prior to the onset of carbonylation. Crystallographic characterization demonstrated that the complexes Fe-3(S2C3H6)(3)(CO)(4)(PEt3)(2) and PBnPh3[Fe-3(S2C3H6)(4)(CO)(4)] feature high-spin ferrous and low-spin ferric as the central metal, respectively.