American Chemical Society
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A Vanadium-Containing Iron−Sulfur Cluster with a V2Fe2S4 Cubane-like Core. Synthesis, Structure, and Characterization of (Et4N)[V2Fe2S4(Me2dtc)5]

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journal contribution
posted on 1997-01-15, 00:00 authored by Yuheng Deng, Qiutian Liu, Yu Yang, Youtong Wang, Yuanba Cai, Daxu Wu, Changneng Chen, Daizheng Liao, Beisheng Kang, Jiaxi Lu
A cubane-type cluster (Et4N)[V2Fe2S4(Me2dtc)5] (1) has been synthesized from an assembly system VS43-/FeCl2/Me2dtc-/PhS- in acetonitrile (Me2dtc- = dimethyldithiocarbamate). The compound 1·2CH3CN crystallizes in the monoclinic space group P21/c (No. 14), with a = 12.174(3) Å, b = 22.135(4) Å, c = 19.712(5) Å, β = 105.43(2)°, V = 5120.3 Å3, ρcalcd = 1.50 g/cm3, and Z = 4. The structure was solved from 6336 unique reflections (I > 3σ(I)) and refined by a full-matrix least-squares method to R = 0.053. The cluster anion contains a cubane-like [V2Fe2S4]4+ core, in which the V−V, Fe−Fe, and V−Fe(mean) distances of the V2Fe2 tetrahedron are 2.745(2), 2.681(1), and 2.780(6) Å, respectively. The Mössbauer effect and the structural parameters indicate that the oxidation states of the Fe and V atoms in the [V2Fe2S4]4+ core are both +3. The 1H NMR shows the paramagnetism of the cluster. The chemical shift of 51V NMR was observed at −391 ppm. The FAB-MS behavior of the cluster indicates the bond breaking of the cluster core.