高等学校化学学报

高等学校化学学报 ›› 2003, Vol. 24 ›› Issue (7): 1150.

• 论文 • 上一篇    下一篇

簇合物裂解法合成二硫纶化合物

严泽民, 王昕, 卞国庆, 戴洁, 朱琴玉, 樊建芬   

  1. 苏州大学化学化工学院, 苏州 215006
  • 收稿日期:2002-08-06 出版日期:2003-07-24 发布日期:2003-07-24
  • 通讯作者: 戴洁(1955年出生),男,博士,教授,从事配位化学、分子组装化学及分子材料研究.E-mail:daijie@suda.edu.cn E-mail:daijie@suda.edu.cn
  • 基金资助:

    国家自然科学基金(批准号:20071024);江苏省教委自然科学基金(批准号:00KJB150001)资助

Studies on Cluster-cracking Method for Synthesizing Dithiolate Complexes

YAN Ze-Min, WANG Xin, BIAN Guo-Qing, DAI Jie, ZHU Qin-Yu, FAN Jian-Fen   

  1. Department of Chemistry and Chemical Engineering, Suzhou University, Suzhou 215006, China
  • Received:2002-08-06 Online:2003-07-24 Published:2003-07-24

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摘要： 以[Me4N]2[M4(SPh)10]和[Me4N]4[S4M10(SPh)16](M=Cd,Zn)为前驱体,采用簇合物裂解法合成了配合物(Bu4N)2[Cd(mnt)2]、(Bu4N)2[M(dmit)2](M=Cd,Zn)以及双核配合物(Me4N)2[Zn2(Sph)2·(S2TTF(SCH2)2)2].运用PM3计算方法得到了各种二硫纶盐配体中硫负离子的静电荷大小关系:mnt2->SPh->dmit2->[(MeS)2TTFS2]2-≈[(CH2S)2TTFS2]2-.在理论计算及实验结果的基础上,探讨了配体上硫负离子的静电荷大小与反应产物间的关系.

关键词: 二硫纶配合物, 四硫代富瓦烯, 簇合物裂解, 锌配合物, 镉配合物

Abstract: Mononuclear complexes (Bu4N)2 [Cd(mnt)2], (Bu4N)2 [M(dmit)2](M=Cd, Zn) and binuclear complex (Me4N)2 [Zn2(Sph)2(S2TTF(SCH2)2)2] were synthesized by cluster-cracking reaction from precursors 2 [M4(SPh)10] and 4 [S4M10(SPh) 16](M=Cd, Zn). The net charge on mercapto sulfurs of these dithiolate ligands was calculated by the methods of quantum chemistry PM3 and resulted in the order: mnt 2->SPh ->dmit 2-> [(MeS)2TTFS2]2-≈ [(CH2S)2TTFS2]2-. Based on these theoretical and experimental results, the relationship between the charge on mercapto sulfurs and the reaction products was discussed.

Key words: Dithiolate, Tetrathiafuvalene, Cluster-cracking, Zinc complex, Cadmium complex

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