化学学报 ›› 1996, Vol. 54 ›› Issue (1): 45-50. 上一篇    下一篇

研究论文

四面体异核金属羰基簇合物的合成、表征及单晶结构分析

武和平;殷元骐;金道森;荣小荥   

  1. 中国科学院兰州化学物理研究所;中国科学院福建物质结构研究所;中国科学院结构化学国家重点实验室
  • 发布日期:1996-01-15

Synthesis, characterization and crystal structure analysis of tetrahedral hetero-metal carbonyl clusters

WU HEPING;YIN YUANQI;JIN DAOSEN;RONG XIAOXING   

  • Published:1996-01-15

利用金属交换反应, 使金属羰基配合物PhCCo~3(CO)~9和过渡金属配合物NaMo(CO)~3(RCp)在THF中回流反应, 制备出三个新的异核三金属羰基簇合物PhCCo~2Mo(CO)~8(RCp)(R=HCO, CH~3CO, C~2H~5O~2C)。结果表明, 与金属交换剂NaMo(CO)~3Cp相比较, 环戊二烯上吸电子基团C=O的存在减弱了金属交换剂NaMo(CO)~3(RCp)的交换活性。同时发现加热可加速该反应向产物的转化以及进一步证明了该金属交换反应的普遍性。对合成的簇合物进行了元素分析, 红外和氢的核磁谱的结构表征。对簇合物PhCCo~2(CO)~8(C~2H~5O~2CCp)的单晶进行了X射线结构测定, 该晶体属于单斜晶系, 空间群为P2~1/c, 晶胞参数: α=1.1356(2)nm,b=1.4030(2)nm, c=1.6076(3)nm, β=107.19(1)°, Z=4。D~c=1.80g/cm^3,R=0.048, Rw=0.057。

关键词: 结构分析, 交换反应, 过渡金属络合物, 单晶结构, 其它基金, 四面体簇合物, 过渡金属羰基化合物

Three new tetrahedral hetero-metal carbonyl clusters were synthesized by refluxing a solution of precursor PhCCo~3(CO)~9 with complexes NaMo(CO)~3(RCp)(R=HCO, CH~3CO, C~2H~5OCO) in THF using metal exchange reaction. Compared with metal exchange reagent NaMo(CO)~3Cp, the results exhibited the electron-withdrawing group C=O on cyclopentadienyl decrease exchange activity of metal exchange reagent NaMo(CO)~3(RCp) and conversion degree to product was accelerated thermally. The results further showed the generality of this kind of metal exchange reaction. The clusters were characterized by C/H analysis, IR and ^1H NMR spectra and X-ray structure determination of cluster PhCCo~2Mo(CO)~8(C~2H~5OCOCp). This cluster is monoclinic space group P2~1/c with α=1.1356(2)nm, b=1.4030(2)m, c=1.6076(3)nm, β=107.19(1)°, Z=4, D~c=1.80g/cm^3, R=0.048 and Rw=0.057.

Key words: STRUCTURAL ANALYSIS, EXCHANGE REACTION, TRANSITION METAL COMPLEX

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