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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Addition of CF(2)group to endohedral fullerene Sc3N@I-h-C-80
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Addition of CF(2)group to endohedral fullerene Sc3N@I-h-C-80

机译：加入CF（2）组至Endohedral Fullerene SC3N @ I-H-C-80

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摘要

We report the first successful synthesis of a CF(2)derivative of the stable endohedral fullerene Sc3N@I-h-C-80. Reaction with CF2ClCOONa yields a singleC(s)-symmetric Sc3N@C-80(CF2) adduct where the CF(2)group is inserted into a [6,6]-bond and opens it to 2.3 angstrom between the bridgehead carbon atoms. As evidenced by absorption and fluorescence spectroscopy as well as cyclic voltammetry, both the HOMO and the LUMO level of Sc3N@C-80(CF2) are slightly (ca.0.1 eV) downshifted with respect to the parent Sc3N@I-h-C-80, so the HOMO-LUMO gap remains essentially unchanged. The DFT calculations suggest that the reaction mechanism is not the previously assumed [2 + 1]-cycloaddition of :CF(2)carbene but rather nucleophilic addition of CF(2)Cl(-)anion followed by elimination of Cl(-)and closing of the CF(2)bridgeviaintramolecular nucleophilic substitution. Selective formation of the [6,6]-Sc3N@C-80(CF2) turns out to be kinetically controlled and promoted by a particular orientation of the endohedral Sc3N cluster with respect to the CF(2)Cl(-)addition site. In its turn, the CF(2)addend partly hampers the rotation of Sc3N the endohedral cluster compared to its quasi-free reorientations in the parent Sc3N@I-h-C-80.
机译：我们报告了稳定的胚乳富勒烯SC3N @ I-H-C-80的CF（2）衍生物的首次成功合成。与CF2Clcoona的反应产生单次-MMETRICS SC3N @ C-80（CF2）加合物，其中CF（2）组插入A [6,6] - 粘合中，并在桥头碳原子之间打开至2.3埃。如通过吸收和荧光光谱和循环伏安法所证明的，SC3N @ C-80（CF2）的HOMO和LUMO水平略微（CA.0.1eV），相对于父SC3N @ IHC-80，所以Homo-Lumo差距基本上没有变化。 DFT计算表明，反应机制不是先前假定的[2 + 1] -cycloaddition：CF（2）卡贝烯，但相当亲核加入CF（2）Cl（ - ）阴离子，然后消除Cl（ - ）和结束CF（2）桥凡氏菌聚核酸替代。选择性形成[6,6] -SC3N @ C-80（CF2），旨在通过对CF（2）Cl（ - ）加成位点的特定方向的特定取向来动力控制和促进。轮到它，CF（2）加法员部分妨碍了SC3N的旋转了EndoheDral集群与父SC3N @ I-H-C-80中的无准重值相比。

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