A new class of binuclear and trinuclear iron-sulfur clusters derived from bis[bis(trimethylsilyl)amido]iron(II)

The compound Fe[N(SiMe 3) 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(SiMe 3) 2) 2(THF) 2] ( 1); with 0.5 equiv of adamantane-1-thiol, [Fe 2(mu 2-S-1-Ad)(mu 2-N(SiMe 3) 2)(N(SiMe 3) 2) 2] ( 2) is formed. The clusters [Fe 3(mu 3-Q)(mu 2-SR) 3(N(SiMe 3) 2) 3] are available by three methods: (i) self-assembly in the systems Fe[N(SiMe 3) 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 [Fe 3Se(S- p-tol) 3(N(SiMe 3) 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 Fe 2S 2 and Fe 2SN rhombs. Clusters 3- 5 contain a mixed-valence Fe 3Q(SR) 3 core with trigonal (cuboidal) geometry. Of known iron-sulfur clusters, these most closely resemble previously reported [Fe 3S(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.