Radical coupling reaction of paramagnetic endohedral metallofullerene La@C82.
Radical coupling reaction of paramagnetic endohedral metallofullerene La@C82.
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DOI：
10.1021/ja802748q
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发表时间：
2008-12
影响因子：
15
通讯作者：
Yuta Takano;A. Yomogida;Hidefumi Nikawa;M. Yamada;T. Wakahara;T. Tsuchiya;Midori O. Ishitsuka;Y. Maeda;T. Akasaka;Tatsuhisa Kato;Z. Slanina;N. Mizorogi;S. Nagase
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文献类型：
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作者：
Yuta Takano;A. Yomogida;Hidefumi Nikawa;M. Yamada;T. Wakahara;T. Tsuchiya;Midori O. Ishitsuka;Y. Maeda;T. Akasaka;Tatsuhisa Kato;Z. Slanina;N. Mizorogi;S. Nagase
La@C(82)（C(2v)）与3-三苯基甲基-5-恶唑烷酮(1)在甲苯中的热反应生成苄基单加合物La@C(82)(C(2v))(CH(2)C(6)H(5)) （2a-2d）。在不存在1的情况下，通过在甲苯中光照射La@C(82)（C(2v)）也可以得到相同的单加合物。这些反应适用于顺磁性金属富勒烯，如La@C(82)（C(s)）和Ce@C(82)（C(2v)）。在α， α,2,4-四氯甲苯存在下，La@C(82)（C(2v)）在1,2-二氯苯中的光照射也得到单加合物La@C(82)(C(2v))(CHClC(6)H(3)Cl(2)) （3a-3d）。单加合物通过光谱分析得到了充分的表征。单晶x射线三维结构分析揭示了其独特的结构。理论计算表明，具有高自旋密度的笼型碳被自由基选择性地攻击，形成由碳碳单键连接的单加合物。与甲苯中的反应不同，La@C(82)（C(2v)）与1在苯中热反应生成金属富勒吡咯烷La@C(82)(C(2v))(C(2)H(4)NCPh(3))(5)。
The thermal reaction of La@C(82)(C(2v)) with 3-triphenylmethyl-5-oxazolidinone (1) in toluene affords benzyl monoadducts La@C(82)(C(2v))(CH(2)C(6)H(5)) (2a-2d). The same monoadducts are also obtained by the photoirradiation of La@C(82)(C(2v)) in toluene without the existence of 1. These reactions are applicable to paramagnetic metallofullerenes, such as La@C(82)(C(s)) and Ce@C(82)(C(2v)). The photoirradiation of La@C(82)(C(2v)) in 1,2-dichlorobenzene in the presence of alpha,alpha,2,4-tetrachlorotoluene also affords the monoadducts La@C(82)(C(2v))(CHClC(6)H(3)Cl(2)) (3a-3d). The monoadducts are fully characterized by spectroscopic analyses. Single-crystal X-ray structure analysis for 3d reveals the unique structure. Theoretical calculations show that the cage carbons having high spin densities are selectively attacked by radical species to form the monoadducts linked by a carbon-carbon single bond. The thermal reaction of La@C(82)(C(2v)) with 1 in benzene affords metallofulleropyrrolidine La@C(82)(C(2v))(C(2)H(4)NCPh(3)) (5), unlike the reaction in toluene.