Zimmermann Christian, Anson Christopher E, Eckermann Amanda L, Wunder Markus, Fischer Gerda, Keilhauer Ilka, Herrling Erik, Pilawa Bernd, Hampe Oliver, Weigend Florian, Dehnen Stefanie
Institut für Anorganische Chemie, Universität Karlsruhe (TH), D-76128 Karlsruhe, Germany.
Inorg Chem. 2004 Jul 26;43(15):4595-603. doi: 10.1021/ic034876t.
By reacting 1-aminoethylammonium (H2NCH2CH2NH3+ = enH+) salts of [Sn2E6]4- anions (E = S, Se), [enH]4[Sn2S6] (1) and [enH]4[Sn2Se6] x en (2), with FeCl2/LiCp, three novel (partly) oxidized, Cp* ligated iron chalcogenide clusters were synthesized. Two of them, [(CpFe)3(mu3-S)2] (3) and [(CpFe)3(mu3-Se)2] (4), contain formally 47 valence electrons. [(CpFe)3(SnCl3)(mu3-Se)4] x 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 [Fe3E2] clusters (E = S, Se) was confirmed by density functional (DFT) investigations, mass spectrometry, cyclic voltammetry and a susceptibility measurement of 3.
通过使[Sn2E6]4-阴离子（E = S，Se）的1-氨基乙铵盐（H2NCH2CH2NH3+ = enH+），即[enH]4[Sn2S6]（1）和[enH]4[Sn2Se6]·en（2），与FeCl2/LiCp反应，合成了三种新型的（部分）氧化的、由Cp配体连接的铁硫属化物簇合物。其中两种，[(CpFe)3(μ3-S)2]（3）和[(CpFe)3(μ3-Se)2]（4），形式上含有47个价电子。[(Cp*Fe)3(SnCl3)(μ3-Se)4]·DME（5）代表了首个已知的混合金属Fe/Sn/Se异立方烷型簇合物。通过单晶X射线衍射对化合物3 - 5进行了结构表征，并通过密度泛函（DFT）研究、质谱、循环伏安法以及对3的磁化率测量，证实了[Fe3E2]簇合物（E = S，Se）的奇价电子数。
