SYNTHESES OF CLOSO-CP'(2)(CO)(3)FE(2)MS(2) CLUSTERS (CP'=ETA(5)-C(5)ME(5) M=FE, RU) AND MOLECULAR-STRUCTURE OF CP'(2)(CO)(3)FE3S2

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 configura tion in which the three iron atoms form a slightly distorted triangle with two mu(3)-S ligands occupying apical positions. Two of the iron a toms 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 ex amples of close clusters having {Fe(2)MS(2)} cores (M = Fe, Ru). Cryst allographic data for Cp'(2)(CO)(3)Fe3S2 (2) are as follows: C23H30- Fe 3O3S2, monoclinic, space group P2(1)/a, a 18.174(2) Angstrom, b = 10.1 159 (9) Angstrom, c 14.317(1) Angstrom, beta = 106.42(1)degrees, V = 2 542.4(4) Angstrom(3), Z = 4, and R = 0.060 for 6221 reflections with \ F-o\ > 3 sigma(F-o).