Reactions of Cp’2Fe2S4 (1) with iron carbonyls (Fe(CO)(5), Fe-2(CO)(9), and Fe-3(CO)(12)) gave Cp’(2)(CO)(3)Fe3S2 (2), and that with Ru-3(Co)(12), Cp’(2)(CO)(3)Fe2RuS2 (3) An X-ray crystal structure analysis of 2 revealed that the {Fe3S2} core has a trigonal bipyramidal configuration in which the three iron atoms form a slightly distorted triangle with two mu(3)-S ligands occupying apical positions. Two of the iron atoms bear an eta(5)-Cp’ ligand, and the third iron atom is coordinated by three terminal carbonyl ligands. Clusters 2 and 3 are the first examples of close clusters having {Fe(2)MS(2)} cores (M = Fe, Ru). Crystallographic data for Cp’(2)(CO)(3)Fe3S2 (2) are as follows : C23H30- Fe3O3S2, monoclinic, space group P2(1)/a, a 18.174(2) Angstrom, b = 10.1159 (9) Angstrom, c 14.317(1) Angstrom, beta = 106.42(1)degrees, V = 2542.4(4) Angstrom(3), Z = 4, and R = 0.060 for 6221 reflections with F-o > 3 sigma(F-o).