Halogenated Benzene Cation Radicals
Halogenated Benzene Cation Radicals
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DOI：
10.1002/ejoc.201201691
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发表时间：
2013-05-01
影响因子：
2.8
通讯作者：
Seppelt, Konrad
中科院分区：
文献类型：
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作者：
Molski, Matthias J.;Khanfar, Monther A.;Seppelt, Konrad
苯阳离子自由基[C_6F_5-CF_3]（+）、[1，4-C_6F_4（CF_3）（2）]（+）、[1，2，4，5-C_6H_2Cl_4]（+）、[C_6F_5-C_6F_5]（+）和[C_6Br_6]（+）与氟砷和氟锑抗衡离子形成盐。通过单晶结构测定得到了它们的结构，并得到了ESR测量和DFT计算的支持。[C6 F5-CF 3]（+）、[1，4-C6 F4（CF 3）（2）]（+）和[1，2，4，5-C6 H2 Cl 4]（+）具有预测的双烯丙基型结构。[C6 F5-C6 F5]（+）可以被描述为具有醌型形式，与中性C6 F5-C6 F5相比，其具有加强的中心C-C键和较小的二面角。[C6 Br 6]（+）是[C6 F6]（+）、[C6 Cl 6]（+）和[C6 I6]（+）之间缺失的连接。它具有Jahn-Teller畸变，虽然比[C6 F6]（+）和[C6 Cl 6]（+）弱，但与[C6 I6]（+）相反，它保持正六边形结构。
The benzene cation radicals [C6F5-CF3](+), [1,4-C6F4(CF3)(2)](+), [1,2,4,5-C6H2Cl4](+), [C6F5-C6F5](+), and [C6Br6](+) have been obtained as salts with fluoroarsenic and fluoroantimony counterions. Their structures have been obtained by single-crystal structure determinations, and supported by ESR measurements and DFT calculations. [C6F5-CF3](+), [1,4-C6F4(CF3)(2)](+), and [1,2,4,5-C6H2Cl4](+) have the predicted bisallyl type structure. [C6F5-C6F5](+) can be described as having a quinoid form with a strengthened central C-C bond and a smaller dihedral angle as compared to the neutral C6F5-C6F5. [C6Br6](+) is the missing link between [C6F6](+), [C6Cl6](+), and [C6I6](+). It has a Jahn-Teller distortion, though weaker than [C6F6](+) and [C6Cl6](+), in contrast to [C6I6](+), which remains in a regular hexagon structure.