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对单电子溴键复合物H3C…Br—Y(Y=H,CCH,CN,NC,C2H3)的结构与性质进行了理论研究.在B3LYP/6-311++G**水平上计算了稳定构型并做了频率分析.BSSE矫正的相互作用能(EBSSE)和NBO及AIM分析输入的波函数在MP2/6-311++G**水平下完成.复合物H3C…Br—Y中,CH3(供电子体)自由基均提供一未成对电子与Br—Y中Br(受电子体)形成了单电子溴键,此单电子溴键也具有“三电子”键的特征.单电子溴键的形成导致甲基H的背向Y弯曲和Br—Y键的拉长及红移单电子溴键复合物的产生.考察了电子受体中不同取代基,C(spn)-Br杂化及溶剂的存在对复合物作用的影响,将单电子氢键,单电子卤键和单电子锂键的作用强度做了对比,进一步对Popelier提出的氢键体系中的前三个重要拓扑指标在单电子溴键体系中的重现性进行了探讨.
The structure and properties of single electron-bromine bond H3C ... Br-Y (Y = H, CCH, CN, NC, C2H3) have been studied theoretically. The stability at B3LYP / 6-311 ++ G ** CONFIGURATION AND FREQUENCY ANALYSIS The wave functions of the BSSE corrected interaction energy (EBSSE) and the NBO and AIM analysis inputs were performed at the level of MP2 / 6-311 ++ G ** In complexes H3C ... Br-Y, CH3 (donor) free radicals both provide an unpaired electron and Br-Y Br (electron acceptor) form a single electron-bromine bond, the single electron bromine bond also has a “three electron ” key characteristics. The formation of electron-bromine bond leads to the back-bending of methyl H and the elongation of Br-Y bond and the generation of red-shifted single electron-bromine bond. The effects of different substituents on electron acceptor such as C (spn) -Br The effects of the hybridization and solvent on the interaction of the complexes were compared. The intensities of the single electron hydrogen bond, the single electron halogen bond and the single electron lithium bond were contrasted. Furthermore, the first three important topologies in the hydrogen bonding system proposed by Popelier Reproducibility of the indicator in the single electron-bromine bond system is discussed.