Synthetic Chemistry and Materials Chemistry of Functionalized Fullerenes

功能化富勒烯的合成化学和材料化学

• 批准号: 13440187
• 负责人: MASAYA Sawamura
• 金额: $ 9.66万
• 依托单位: Hokkaido University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13440187/
• 关键词: Fullerene; Ferrocene; Vesicle; Liquid Crystal; Organocopper; Cbo; C70; Functional Materials; Cp配位子; 有機銅化合物; フェロモン; 錯体触媒; メタロセン; 触媒; 分子集合体; エピタキシャル成長

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.

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。该反应产生嵌入[60]富勒烯球形表面的环戊二烯。新分子中的环戊二烯由[60]富勒烯的十二个五边形之一组成，并被带有来自有机铜试剂的苯基取代基的五个sp3碳原子包围。环戊二烯结构可通过碱去质子化转化为6-π电子环戊二烯基阴离子。含有五碳配体环戊二烯基（Cp）的金属配合物在有机金属化学中发挥着非常重要的作用。本研究旨在通过此类功能化富勒烯合成可用作催化剂和材料的功能分子。本研究的结果是，有机铜试剂向富勒烯的多次添加得到了显着改进，使得可以大规模定量产率合成各种具有不同有机取代基的富勒烯衍生物。合成了富勒烯（C60 和 C70）和二茂铁的杂化物。发现环戊二烯基型富勒烯的碱金属盐可溶于水并且它们形成球形双层囊泡。还合成了具有液晶性质的衍生物和双层Cp型化合物。

项目成果

Takashi Shimada: "Epitaxial Growth and Electronic Structure of a C_<60> Derivative Prepared by Using a Solution Spray Technique"J. Appl. Phys.. 90・1. 209-212 (2001)

岛田隆：“使用溶液喷雾技术制备的C_<60>衍生物的外延生长和电子结构”J.Appl. 90・1（2001）

E.Nakamura: "Synthesis, Structure, and Aromaticity of a Hoop-Shaped Cyclic Benzenoid [10]Cyclophenacene"J.Am.Chem.Soc.. 125. 2834-2835 (2003)

E.Nakamura：“环状苯环[10]环苯并烯的合成、结构和芳香性”J.Am.Chem.Soc.. 125. 2834-2835 (2003)

Masaya Sawamura: "Regioselective penta-addition of 1-alkeny1 copper reagent to [60]fullerene. Synthesis of penta-alkeny1 FCp ligand"Journal of Organmetallic Chemistry. 652巻. 31-35 (2002)

Masaya Sawamura：“1-烯基 1 铜试剂与 [60] 富勒烯的区域选择性五加成。五烯基 1 FCp 配体的合成”《有机金属化学杂志》652. 31-35 (2002)。

Eiichi Nakamura: "Chemistry of y^5-Fullerene Metal Complexes"Pune Appl. Chem.. 73・2. 355-359 (2001)

中村英一：“y^5-富勒烯金属配合物的化学”Pune Chem.. 73・2。

T.Shimada: "Epitaxial Growth and Electronic Structure of a C_<60> Derivative Prepared by Solution Spray Technique"Appl.Phys.Lett.. 90. 209-212 (2001)

T.Shimada：“通过溶液喷雾技术制备的 C_<60> 衍生物的外延生长和电子结构”Appl.Phys.Lett.. 90. 209-212 (2001)