高等学校化学学报

高等学校化学学报 ›› 1999, Vol. 20 ›› Issue (8): 1172.

• 论文 • 上一篇    下一篇

新型双四面体过渡金属簇合物的合成与表征

张(丰刀女)1, 陈学年1, 丁二润1, 殷元骐1, 孙杰2   

  1. 1. 中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室, 兰州 730000;
    2. 中国科学院兰州化学物理研究所羰基合成, 上海 200032
  • 收稿日期:1998-10-06 出版日期:1999-08-24 发布日期:1999-08-24
  • 通讯作者: 殷元骐
  • 作者简介:张(丰刀女),男,35岁,博士研究生.
  • 基金资助:

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

Synthesis and Characterization of Novel Double Tetrahedral Transition Metal Clusters

ZHANG Jie1, CHEN Xue-Nian1, DING Er-Run1, YIN Yuan-Qi1, SUN Jie2   

  1. 1. State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China;
    2. Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
  • Received:1998-10-06 Online:1999-08-24 Published:1999-08-24

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被引次数

2

摘要： 利用Co2(CO)8与[Cl3CC(O)OCH2]2的反应合成了以C(O)OCH2CH2OC(O)桥联两个Co3C四面体骨架为特征的新型双四面体簇合物[(CO)9Co3(μ3-C)C(O)OCH2]2(1);1与不同物质的量比的Na[M(CO)3C5H4R](M=Mo,W;R=H,C(O)Me)反应,得到一步交换的产物(CO)9Co3(μ3-C)C(O)OCH2CH2OC(O)(μ3-C)Co2M(CO)8(C5H4R)[M=Mo,R=H(2);M=Mo,R=C(O)Me(3);M=W,R=H(4);M=W,R=C(O)Me(5)]或两步交换的产物[(C5H4R)(CO)8Co2M(μ3-C)C(O)OCH2]2[M=Mo,R=H(6);M=Mo,R=C(O)Me(7);M=W,R=H(8);M=W,R=C(O)Me(9)].5或9分别与Na[Mo(CO)3C5H5]以12的物质的量比反应得到含一个手性四面体骨架(CoMoWC)的(C5H5)(CO)8Co2Mo(μ3-C)C(O)OCH2CH2O·C(O)(μ3-C)CoMoW(CO)7(C5H4C(O)Me)(C5H5)(10)或含两个手性四面体骨架(CoMoWC)的[(C5H5)(C5H4C(O)Me)(CO)7CoMoW(μ3-C)C(O)OCH2]2(11);对化合物1_11进行了CH元素分析、IR和1HNMR等表征.结果表明,在金属交换反应中处于不同簇环境下的Co(CO)3基团反应活性不同.对化合物1进行了晶体X射线衍射分析.化合物1的晶体属单斜晶系,P21/n(#14)空间群,晶胞参数a=0.933 0(2)nm,b=1.519 7(4)nm,c=1.178 3(4)nm,=91.16(2)°,Z=2,F(000)=972.分子结构呈中心对称.

关键词: 合成, 晶体结构, 双四面体簇合物, 金属交换反应

Abstract: The reaction of Co2(CO)8 and [C13CC(O)OCH2]2 gave a novel double tetrahedral cluster compound([(CO)9Co3(μ3-C)C(O)OCH2]2 1)containing two tetrahedral skeletons(Co3C) linked by a C(O)OCH2CH2OC(O) bridge. The reaction of 1 with different molecular ratios of Na[M(CO)3C5H4R][M=Mo, W; R=H, C(O)Me] gave the one-step exchange products (CO)9Co3(μ3-C)C(O)OCH2CH2OC(O)(μ3-C)Co2M(CO)8(C5H4R)[M=Mo, R=H(2); M=Mo, R=C(O)Me (3); M=W, R=H (4); M=W, R=C(O)Me (5)] or the two-step exchange products or the two-step exchange products [(C5H4R)(CO)8Co2M(μ3-C)C(O)OCH2]2[M=Mo, R=H(6); M=Mo, R=C(O)Me (7); M=W, R=H (8); M=W, R=C(O)Me (9)]. By treating. By treating5 or 9 with Na[Mo(CO)3C5H5] in 1/2 molecular ratio, the compound (C5H5)(CO)8Co2Mo(μ3-C)·C(O)OCH2CH2OC(O)(μ3-C)CoMoW(CO)7(C5H4C(O)Me)(C5H5)(10) or [(C5H5)(C5H4·C(O)Me)(CO)7CoMoW(μ3-C)C(O)OCH2]2 (11) which has one or two chiral tetrahedral skeletons(CoMoWC)was obtained. Compounds 1_11 were characterized by C/Hanalyses, IRand 1HNMR. The results indicate that the Co(CO)31/n (#14) and lattice parameters, a=0.9330(2) nm, b=1.5197(4) nm, c=1.1783(4) nm, β=91.16(2)°, Z=2, F (000)=972.

Key words: Synthesis, Crystal structure, Double tetrahedral cluster, Metal exchange reaction

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