Preparation, Structural Determination, and Characterization of Electronic Properties of [5,6]- and [6,6]-Carbosilylated Sc3N@Ih -C80
Preparation, Structural Determination, and Characterization of Electronic Properties of [5,6]- and [6,6]-Carbosilylated Sc3N@Ih -C80
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[5,6]-和[6,6]-碳甲硅烷基化Sc3N@Ih -C80的制备、结构测定和电子性质表征
DOI：
10.1002/asia.201700506
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发表时间：
2017
期刊：
影响因子：
--
通讯作者：
Akasaka Takeshi
中科院分区：
文献类型：
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作者：
Kako Masahiro;Sugiura Takeshi;Miyabe Kyosuke;Yasui Masanori;Yamada Michio;Maeda Yutaka;Guo Jing-Dong;Nagase Shigeru;Akasaka Takeshi
Sc 3 N @ Ih-C80与硅烷1的光化学碳硅烷化得到两个相应的[5，6]-加合物2和3以及一个[6，6]-加合物4。通过光谱、电化学和理论方法对产物的结构和电子性质进行了表征。通过单晶X射线晶体学分析揭示了2的结构。观察到3到2的热异构化，而2到3的热异构化在100 °C下进行得不太有效。在相同条件下加热时，加合物4经历容易的分解以提供Sc 3 N @ Ih-C80，或异构化成少量的2和3。通过理论计算结果对2、3、4的相对稳定性进行了合理化。相比之下，加合物2、3和4在用于甲硅烷基化的光解条件下是稳定的。Sc 3 N @ Ih-C80的光化学官能化代表了获得热不稳定富勒烯基产品的方便合成方法。
Photochemical carbosilylation of Sc3N@Ih‐C80with silirane1afforded two corresponding [5,6]‐adducts,2and3, and a [6,6]‐adduct,4. The structural and electronic properties of these products were characterized by means of spectroscopic, electrochemical, and theoretical methods. The structure of2was disclosed by means of single‐crystal X‐ray crystallographic analysis. Thermal isomerization of3to2was observed, whereas that of2to3proceeded less efficiently at 100 °C. Upon heating under the same conditions, adduct4underwent facile decomposition to afford Sc3N@Ih‐C80, or isomerized into small amounts of2and3. The relative stabilities of2,3, and4were rationalized through the results of theoretical calculations. In contrast, adducts2,3, and4were stable under the photolytic conditions employed for carbosilylation. The photochemical functionalization of Sc3N@Ih‐C80represents a convenient synthetic method to obtain thermally labile fullerene‐based products.