The compound Fe[N(SiMe3)(2)](2) is shown to be a useful precursor to dinuclear and trinuclear iron-sulfur-silylamido complexes by reaction with thiols or thiols and sulfur in tetrahydrofuran (THF) or toluene. Reaction with 1 equiv of p-tolylthiol affords [Fe-2(mu(2)-S-p-tol)(2)(N(SiMe3)(2))(2)(THF)(2)] (1); with 0.5 equiv of adamantane-1-thiol, [Fe-2(mu(2)-S-1-Ad)(mu(2)-N(SiMe3)(2))(N(SiMe3)(2))(2)] (2) is formed. The clusters [Fe-3(mu(3)-Q)(mu(2)-SR)(3)(N(SiMe3)(2))(3)] are available by three methods: (i) self-assembly in the systems Fe[N(SiMe3)(2)](2)/RSH/S or Se [Q = S, R = p-tol (3) and 1-Ad (5)]; (ii) reaction of 1 with Q = S or Se to yield 3 or [Fe3Se(S-p-tol)(3)(N(SiMe3)(2))(3)] (4); (iii) reaction of 2 with 1-AdSH and S to give 5. Structures of 1-5 are presented. Complexes 1 and 2 contain planar Fe2S2 and Fe2SN rhombs. Clusters 3-5 contain a mixed-valence Fe(3)Q(SR)3 core with trigonal (cuboidal) geometry. Of known iron-sulfur clusters, these most closely resemble previously reported [Fe3S(S-R-S)(3)](2-) stabilized by bidentate thiolate ligands. Complexes 1-5, together with a small set of recently described clusters of nuclearities 2, 4, and 8, constitute a new class of iron-sulfur-silylamido clusters. Complexes 3-5 constitute a new structure type of mixed-valence iron-sulfur clusters.