Neue Synthesewege zu neutralen gemischtsubstituierten Eisen-Schwefel-Clustern

The reaction of [Fe(N(SiM e3)2)2] with thiols RSH, elem ental sulfur, and neutral ligands L (with sulfur donor atoms, e.g. thiourea derivatives) gives [Fe4S4(SR )2L2] clusters in high yields. The structure of [Fe4S4(2.4.6-(C3H7)3C6H 2-S)2(dpdm i)2] (dpdmi: diisopropyldim ethylim idazolthion) was determ ined by X-ray crystallography. W hen [Fe4S4I4]2~ is reac ted w ith a large excess o f P M eP h 2 o r P M e2Ph [Fef,S6l 2(P M eP h 2)4] and [Fe6S6I2(P M e 2P h )4], respectively, are o b ta in e d in n early q u a n tita tiv e yield. B asket-like s tru c tu re s o f the [Fe6S6]2+ cores w ere d e te c te d by X -ray s tru c tu re analysis. W hile [Fe4S4(S R )4]2~ cluste rs do no t reac t w ith p h o sp h an es at a m b ien t te m p e ra tu re 2 :2 func tionalized species like [Fe4S4(S R )2(tm tu )2] lead to b ask e t-ty p e c lu s te rs [Fe6SA(S R )2(P R 3)4].