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化学学报
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化学学报 ›› 2005, Vol. 63 ›› Issue (21): 1979-1990. 上一篇    下一篇

研究论文

系列三核钼硫簇合物的合成、结构表征和性质研究

卢绍芳*，孙福侠，朱永宝，彭瑛，梁玉仓，李俊篯，黄子祥，吴锵金，卢灿忠   

  1. (中国科学院福建物质结构研究所 结构化学国家重点实验室 福州 350002)
  • 投稿日期:2005-02-24 修回日期:2005-07-29 发布日期:2010-12-10
  • 通讯作者: 卢绍芳

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

LU Shao-Fang*, SUN Fu-Xia, ZHU Yong-Bao, PENG Ying, LIANG Yu-Cang, LI Jun-Qian, HUANG Zi-Xiang, WU Qiang-Jin, LU Can-Zhong   

  1. (State Key Laboratory of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002)
  • Received:2005-02-24 Revised:2005-07-29 Published:2010-12-10
  • Contact: LU Shao-Fang

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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.

关键词: 三核钼硫原子簇化合物, 芳香基取代配体, 合成, 晶体结构, 谱学表征, 电子结构, 导电性

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.

Key words: trinuclear molybdenum-sulfur cluster, substituted ligand with aryl group, synthesis, crystal structure, spectral characterization, electronic structure, conductivity