大取代环戊二烯基铪的合成与结构分析  

Syntheses and Structure Analysis of Bulkier Substituted Hafanocene Dichlorides

作　　者：王家喜[1] 陈寿山[1] 王序昆[1] 王宏根[2] 

机构地区：[1]南开大学元素有机化学研究所 [2]南开大学中心实验室

出　　处：《化学学报》1993年第5期506-513,共8页Acta Chimica Sinica

基　　金：国家自然科学基金

摘　　要：芳基锂与6,6-二烷基富烯发生加成反应,生成含或不含手性碳的大位阻取代环戊二烯基负离子。用四氯化铪配合,合成了19个大取代茂铪化合物。讨论了其~1HNMR。化合物[(CH_3)_2C(C_6H_4-p-CH_3)-C_5H_4]_2HfCl_2经X射线衍射分析。晶体为单斜晶系,空间群为I2/a,晶胞参数α=2.2263(7),b=0.6674(2),c=2.5379(9)nm,β=135.13(3)°,R=0.058,R_w=0.069,结构研究表明,取代基的引入,使得茂环发生变形,最大扭曲角为8.45°。Aryllithium added with 6, 6-dialkylfulvenes at exocyclic double bond to give bulkier substituted cyclopentadienyl anions with chiral or achiral carbon. Complexed by hafanium chloride nineteen bulkier substituted hafanocene dichlorides would be synthesized, and those ~1H NMR will be discussed. The compound [(CH_3)_2C(C_6H_4-p-CH_3)C_5H_4]_2HfCl_2 has been determined by X-ray diffraction. The crystal is monoclinic, space group I2/α with α= 2.2263(7), b= 0.6674(2), c=2.5377(9)nm, β= 135.13(3)°. R =0.058, R_w=0.069. The result from the structure analysis is that the coming of bulkier substituent make cyclopentadienyl inform and the biggest torsional angle is 8.45°.

关 键 词：戊铪化合物 NMR 晶体结构 

分 类 号：O627.43[理学—有机化学]