Organic Synthesis of Transition Metal Encapsulated Fullerenes

过渡金属封装富勒烯的有机合成

基本信息

批准号：
09650960
负责人：
TOBE Yoshito
金额：
$ 2.18万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1998
项目状态：
已结题

项目摘要

1. Spectroscopic Studies on the Structures of Cyclocarbons : Molecular structures of cyclo[n]carbons (n= 12, 16, 18, 20, and 24), which were generated in the laser-desorption mass spectroscopic method from the corresponding organic precursors, were investigated on the basis of the ultraviolet photoelectron spectra of the cluster anions.It was revealed that the cyclo[n]carbons with 4n carbons possess polyynes structure whereas those with 4n+2 carbons are cumulenic structure.2. Generation of Cage Polyyne (C_<60>H_6) and its Isomerization into Fullerene : A precursor to the cage polyyne C_<60>H_6 was prepared in order to investigate the possibility regarding dehydrogenative isomerization of C_<60>H_6 into C_<60> fullerene.In the laser-desorption mass spectra of the precursor, we observed not only C_<60>H_6 derived from elimination of six indane molecules but also C_<60> fullerene which was formed presumably by the isomerization of the reactive polyyne chain.These results suggest the possible total synthetic pathway of fullerenes and their metal encapsulated derivatives on the basis of polyyne cyclization.3. Generation of Cage Azapolyyne (C_<58>N_2H_4) and its Isomerization into Diazafullerene : The cage polyyne C_<58>N_2H_4 having two pyridine rings was generated from the corresponding organic precursor by the same method as described above.In the laser-desorption mass spectra, we observed not only C_<58>N_2H_4 but also a small peak due to diazafullerene C_<58>N_2.This is an important finding with regard to the synthesis of metal encapsulated fullerenes, because it represents the first observation of this novel heterofullerene which is isoelectronic with fullerene dianion.

1. 环碳结构的光谱研究：环[n]碳（n=12、16、18、20和24）的分子结构，它们是通过激光解吸质谱法从相应的有机前驱体产生的，基于团簇阴离子的紫外光电子能谱进行了研究，揭示了具有4n个碳的环[n]碳具有多炔结构而碳原子数为4n+2的则为积聚结构。2．笼状聚炔(C_60>H_6)的生成及其异构化为富勒烯：制备笼状聚炔C_<60>H_6的前体，以研究C_<60>H_6脱氢异构化为C_<60>的可能性在前驱体的激光解吸质谱中，我们不仅观察到由六个茚满分子消除产生的C_<60>H_6，而且还观察到富勒烯C_<60>富勒烯可能是由反应性多炔链异构化形成的。这些结果提示了基于多炔环化的富勒烯及其金属封装衍生物的可能全合成途径。 3．笼状氮杂多炔(C_ 58 N_2H_4)的生成及其异构化为二氮杂富勒烯：通过与上述相同的方法由相应的有机前体生成具有两个吡啶环的笼状多炔C_ 58 N_2H_4。光谱中，我们不仅观察到 C_<58>N_2H_4，而且还观察到二氮杂富勒烯引起的小峰C_ 58 N_2。这是关于金属封装富勒烯合成的重要发现，因为它代表了这种与富勒烯二价阴离子等电子的新型异富勒烯的首次观察。