Syntheses of the 47 electron clusters [(Cp*Fe)3(mu3-X)2] (X = S, Se) and the First Fe/Sn/Se Heterocubane Cluster [(CpFe)3(SnCl3)(mu3-Se)4] x DME by the use of chalcogenostannate salts.

By reacting 1-aminoethylammonium (H 2 NCH 2 CH 2 NH 3 + = enH + ) salts of [Sn 2 E 6 ] 4 - anions (E = S, Se), [enH] 4 -[Sn 2 S 6 ] (1) and [enH] 4 [Sn 2 Se 6 ].en (2), with FeCl 2 /LiCp*, three novel (partly) oxidized, Cp* ligated iron chalcogenide clusters were synthesized. Two of them, [(Cp*Fe) 3 (μ 3 -S) 2 ] (3) and [(Cp*Fe) 3 (μ 3 -Se) 2 ] (4), contain formally 47 valence electrons. [(Cp*Fe) 3 (SnCl 3 )(μ 3 -Se) 4 ].DME (5) represents the first known mixed metal Fe/Sn/Se heterocubane type cluster. Compounds 3-5 were structurally characterized by single-crystal X-ray diffraction, and the odd valence electron number of the [Fe 3 E 2 ] clusters (E = S, Se) was confirmed by density functional (DFT) investigations, mass spectrometry, cyclic voltammetry and a susceptibility measurement of 3.