新型侧链含吡啶的三氯一茚锆络合物的合成  

Synthesis of Novel Trichloride Indenyl Zirconium Complexes with Pendant Pyridine Moiety

作　　者：张延路[1] 马海燕[1] 黄吉玲[1] 

机构地区：[1]华东理工大学金属有机化学实验室,上海200237

出　　处：《有机化学》2014年第1期197-203,共7页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.20372022)资助项目~~

摘　　要：三氯单茂（茚）锆络合物的合成一直以来都是一个难点，往往伴有双茂（茚）锆络合物的产生. 本工作通过侧链吡啶取代的茚基的锂盐直接与ZrCl4·2THF反应选择性的生成了一类具有螯合环状结构的半夹心三氯一茚锆络合物[Ind-Bridge-Py]ZrCl3·THFx（CN1～CN3），无双茚锆络合物的生成. 与传统单茚锆络合物的合成方法相比，此类吡啶茚锆络合物的合成方法具有操作简单，产物单一且较易分离，产率较高等优点. CN2 [Bridge：C（Me，Et）CH2]单晶证明侧链吡啶的N原子与锆配位，同时络合物晶体中含有两分子四氢呋喃，一分子四氢呋喃中的氧与锆配位，而另一分子则呈游离状态.It is always difficult to synthesize half-sandwich trichloride cyclopentadienyl （indenyl） zirconium complexes due to accompanying the formation of sandwich metallocene （indenyl） zirconium complexes. In this paper, a series of novel trichloride indenyl zirconium complexes, [Ind-Bridge-Py]ZrCl3·THFx （CN1～CN3）, bearing pendant pyridine moiety with chelating ring structure, were synthesized selectively by directly reacting lithium salts of substituted indenyl with ZrCl4·2THF, and no di-indenyl zirconium complexes were formed. Compared with conventional methods of synthesizing half-sandwich indenyl complexes, the synthetic method of these kinds of trichloride indenyl zirconium complexes with pendant pyridine moiety has the advantages of easy operation, single product, easy separation and high yield. The X-ray of CN2 [Bridge： C（Me, Et）CH2] shows that zirconium is coordinated with N atom and also with one O atom from THF. Another molecule of THF in the crystal is free and not coordinated with zirconium.

关 键 词：吡啶 三氯一茚锆 配位 四氢呋喃 

分 类 号：O627.43[理学—有机化学]