Dichlorocarbene addition to C60 from the trichloromethyl anion: carbene mechanism or Bingel mechanism?
Dichlorocarbene addition to C60 from the trichloromethyl anion: carbene mechanism or Bingel mechanism?
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二氯卡宾从三氯甲基阴离子加成C60：卡宾机制还是宾格尔机制？
DOI：
10.1021/jp900265g
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发表时间：
2009
期刊：
影响因子：
--
通讯作者：
Zhongfang Chen
中科院分区：
文献类型：
--
作者：
Xingfa Gao;K. Ishimura;S. Nagase;Zhongfang Chen
采用密度泛函理论（DFT）方法比较研究了C（60）与三氯甲基阴离子(CCl（3)(-)）在宾格尔机制和二氧化碳机制下的反应。与导致C(60)（CCl(2)）形成的二氧化碳机制相比，宾格尔机制具有很强的竞争性。与区域选择性和溶剂敏感性较弱的卡宾反应机制不同，宾格反应机制的唯一产物是[6,6]-C(60)（CCl(2)）异构体，并且有利于高极性溶剂。结果得到了强有力的实验支持，同时也合理化了这些实验结果。
The reactions of C(60) and trichloromethyl anion (CCl(3)(-)) via both the Bingel mechanism and the carbene mechanism were comparably studied by means of density functional theory (DFT) computations. The Bingel mechanism is highly competitive as compared with the carbene mechanism that leads to the formation of C(60)(CCl(2)). Unlike the carbene mechanism with a weak regioselectivity and solvent sensitivity, the Bingel mechanism yields the [6,6]-C(60)(CCl(2)) isomer as the exclusive product and favors highly polar solvents. The results receive strong experimental support and simultaneously rationalize these experimental findings.