Synthetic Chemistry and Materials Chemistry of Functionalized Fullerenes

在我们对富勒烯功能化的研究中，我们发现苯基铜(I)试剂可以一步五次加成到[60]富勒烯上。该反应生成嵌入在[60]富勒烯球面中的环戊二烯。新分子中的环戊二烯由[60]富勒烯的十二个五边形中的一个组成，并被五个SP3碳原子包围，这些碳原子带有来自有机铜试剂的苯基取代基。通过碱去质子化可以将环戊二烯结构转化为6-π电子环戊二烯基阴离子。含五碳配体环戊二烯基(CP)的金属络合物在金属有机化学中具有重要的作用。本研究旨在通过这种功能化的富勒烯来合成可用作催化剂和材料的功能分子，作为本研究的结果，有机铜试剂与富勒烯的多次加成得到了显著的改善，从而可以大规模地定量合成各种不同有机取代基的富勒烯衍生物。合成了富勒烯(C60和C70)与二茂铁的杂化化合物。研究发现，环戊二烯型富勒烯的碱金属盐可溶于水，形成球形双层囊泡。还合成了具有液晶性质的衍生物和双层CP型化合物。

During our studies on fullerene functionalization, we have found a one-step five-fold addition of a phenylcopper(I) reagent to [60]fullerene. This reaction produces a.cyclopenadiene embedded in a spherical surface of [60]fullerene. The cyclopentadiene in the new molecule consists of one of the twelve pentagon of [60]fullerene, and is surrounded by the five sp3 carbon atoms bearing a phenyl substituent derived from the organocopper reagent. The cyclopentadiene structure can be converted into 6-π electron cyclopentadienyl anion through deprotonation by a base. Metal complexes containing a five-carbon ligand cyclopentadienyl (Cp) play very important roles in organometallic chemistry. This study aimed at synthesis of functional molecules useful for applications as catalysts and materials by means of such functionalized fullerenes.As results of this study, the multiple addition of organocopper reagents to fullerenes have been significantly improved so that various fullerene derivatives with different organic substituents can be synthesized in quantitative yields in large scales. Hybrids of fullerenes (C60 and C70) and ferrocene were synthesized. It was found that alkali metal salts of the cyclopentadienyl type-fullerenes are soluble in water and that they forms spherical bilayer vesicles. Derivatives with liquid crystalline properties and double decker Cp-type compounds were also synthesized.