系列三核钼硫簇合物的合成、结构表征和性质研究

系统地报道了9个三核钼硫簇合物的合成和结构表征. 晶体结构分析表明, 其中化合物1和6具有Mo₃(μ₃-S)(μ-S)₃]簇芯, 化合物2和3具有不对称的簇芯Mo₃(μ₃-S)(μ-O)(μ-S)₂], 化合物4, 5, 7和8具有少见的Mo₃(μ₃-O)(μ-S)₃]簇芯, 而化合物9则具有Mo₃(μ₃-S)(μ-S₂)₃]簇芯. 这一系列不同的簇芯以及桥配体和“松散”配位的端配体造成了不同的堆积结构. 讨论了前三种簇芯的电子结构, 并根据它们的立体构型和电子结构对某些重要的谱学表征结果做了合理的诠释. 测定了化合物4的变温电导率, 表明其具有半导体导电性能.

Synthesis, Structural Characterization and Properties of a Series of Trinuclear Molybdenum-sulfur Cluster Compounds

The syntheses, crystal structures as well as the spectral characterizations including IR, Raman, UV-Vis and ⁹⁵Mo NMR of nine trinuclear molybdenum-sulfur cluster compounds were systematically reported. It is shown from the results of the crystal structure analysis that their cluster cores are different. Mo₃(μ₃-S)(μ-S)₃] core is for 1 and 6; Mo₃(μ₃-S)(μ-O)(μ-S)₂] core for 2 and 3, Mo₃(μ₃-O)(μ-S)₃] core for 4, 5, 7, 8 and Mo₃(μ₃-S)(μ-S₂)₃] core for 9. In this paper, the different packing structures for these compounds along with a variety of cluster cores and the peripheral bridging ligands or loosely coordinated terminal ligands were described. The electronic structures of the first three cluster cores were also discussed. Moreover, a rational interpretation for some important spectral results has been made based on their stereo and electronic structures. Finally, the temperature dependence of the electric conductivity of 4 has been measured, indicating that this compound exhibits the electroconductivity of semiconductor.