Synthesis of Functional Organometallic Complexes Involving a Pentahaptofullerene Ligand

涉及五羟基富勒烯配体的功能性有机金属配合物的合成

基本信息

批准号：
09440238
负责人：
SAWAMURA Masaya
金额：
$ 4.16万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
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

The pentaphenylated fullerene anion C_<60>Ph_5-, which is obtained through the five-fold addition of an organocopper reagent to C_<60>, and its metal complexes represent a new class of cyclopentadiene derivatives, which can be prepared through deprotonation of the parent compond. One out of twelve pentagons in C_<60> is isolated from the remaining 50 sp^2 carbon atoms of the C_<60> molecule by five surrounding sp3 carbon atoms each bearing a phenyl group. The previous X-ray crystallographic studies revealed the highly unique cavity structure formed around the cyclopentadienyl (Cp) moiety by the five phenyl groups, but failed to give us information on the electronic properties of these unique molecules. In this research project, we have carried out ab-initio molecular orbital calculations and electrochemical experiments and obtained evidence that there is endohedral homoconjugation, that is, an electronic interaction between the upper Cp and the lower C_<50> moiety in C_<60>Ph_5-and C_<60>Ph_5H through inside of the C_<60> cage.We also found that the reaction of C_<70> with an organ ocopper reagent gives a trisaddition product [C_<7O>Ar_3H, Ar = 4-CF_3-C_6H_4] with an indene-like substructure flanked by the three sp^3 carbons in a quantitative yield. The trisadduct was deprotonated with metal alkoxides to form the corresponding metal complexes C_<70>Ar_3M [M=K, Tl]. The results of ab initio molecular orbital calculations and X-ray diffraction study suggested that C_<70>Ar_3- coordinates to the metal as an eta^5-indenylide rather than a eta^3-ligand in C_<7O>Ar_3M.

五苯基化的富勒烯阴离子C_<60>Ph_5-是通过有机铜试剂与C_<60>五次加成而得到的，其金属配合物代表了一类新的环戊二烯衍生物，可以通过环戊二烯去质子化来制备。父化合物。 C_ 60 中的十二个五边形中有一个通过每个带有苯基的五个周围的sp 3 碳原子与C_ 60 分子的剩余50个sp ^ 2 碳原子隔离。之前的X射线晶体学研究揭示了五个苯基在环戊二烯基（Cp）部分周围形成的高度独特的空腔结构，但未能为我们提供有关这些独特分子的电子特性的信息。在本研究项目中，我们进行了从头算的分子轨道计算和电化学实验，获得了内嵌同共轭的证据，即C_<60>中上部Cp和下部C_<50>部分之间存在电子相互作用。 Ph_5-和 C_<60>Ph_5H 通过 C_<60> 笼内部。我们还发现 C_<70> 与有机铜试剂反应产生三加成产物[C_<7O>Ar_3H, Ar = 4-CF_3-C_6H_4]，具有定量产率的侧翼为三个sp^3碳的茚状子结构。用金属醇盐将三加合物去质子化以形成相应的金属络合物C_ 70 Ar_3M[M＝K，Tl]。从头算的分子轨道计算和X射线衍射研究的结果表明，C_<70>Ar_3-以eta^5-茚基的形式与金属配位，而不是C_<7O>Ar_3M中的eta^3-配体。