高等学校化学学报

高等学校化学学报 ›› 1998, Vol. 19 ›› Issue (5): 760.

• 论文 • 上一篇    下一篇

簇合物Co6S8(PBu3n)6的晶体结构及簇骼M6E8P6(E=S,Se,Te)的协同效应

康北笙1, 陈忠宁1, 苏成勇1, 郑康成1, 刘汉钦1, 周忠远2   

  1. 1. 中山大学化学与化工学院, 广州, 510275;
    2. 中国科学院成都有机化学研究所, 成都, 610041
  • 收稿日期:1997-04-25 出版日期:1998-05-24 发布日期:1998-05-24
  • 通讯作者: 康北笙,女,56岁,博士,教授,博士生导师.
  • 作者简介:康北笙,女,56岁,博士,教授,博士生导师.
  • 基金资助:

    国家自然科学基金;广东省自然科学基金;中国科学院上海有机化学研究所金属有机开放实验室基金

Crystal and Molecular Structure of Co6S8(PBu n3)6 and Synergism in the Cluster Core M6E8P6(E=S, Se, Te)

KANG Bei-Sheng1, CHEN Zhong-Ning1, SU Cheng-Yong1, ZHENG Kang-Cheng1, LIU Han-Qin1, ZHOU Zhong-Yuan2   

  1. 1. School of Chemistry and Chemical Engineering, Zhongshan University, Guangzhou, 510275;
    2. Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu, 610041
  • Received:1997-04-25 Online:1998-05-24 Published:1998-05-24

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摘要： 簇骼为M6E8P6的六核簇合物的一个新成员——Co6S8(PBun3)6的合成和晶体结构表明,可能是由3个单核基元Co(PBun3)2S先组装成三核簇状基元化合物Co3(μ2-S)3(μ3-S)(PBun3)3,然后由2个这样的三核亚单元形成μ3-S桥生成该六核簇合物.讨论了簇骼为[M6E8P6]n(M=Fe,Mo,Co,Cr,W;E=S,Se,Te;n=-1,0,+1,+2,+3)的系列簇合物的分子内协同效应.

关键词: 钴膦硫簇合物, 六核簇合物, 协同效应, 晶体结构

Abstract: Hexanuclear cobalt-sulfur cluster complex Co6S8(PBu3n)6 is a new member of a series of cage like homonuclear clusters with skeleton [M6E8P6]n, in which M=Cr, Mo, W, Fe, Co; E=S, Se, Te; n=-1, 0, +1, +2, +3. The Co6 octahedron and the S8 cubane of the title complex are intercalated to form the cluster core, with the Patoms terminally ligated to Co. The synthetic process and the crystal structure analysis show that the formation process can be viewed as the construction of three mononuclear species Co(PBu3n)2S to form a metastable trinuclear "synthon" Co3(μ2 S)3(μ3 S)(PBu3n)3, two of which then combine to form the final stable cluster Co6S8(PBu3n)6. Synergism within a molecule having skeleton M6E8P6 was discussed from the following viewpoints: ease of cluster formation; high stability towards redox reaction; delocalization of valence electrons; electrons of the reduced states enter the anti-bonding orbitals; and the idea of metal-based valence electrons.

Key words: Cobalt-phosphine-sulfur cluster complexes, Hexanuclear clusters, Synergism effect, Crystal structure

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