氧族桥原子对类立方烷簇[Mo_4X_4Cp_4′]成键特征的影响(X=O,S,Se,Te;Cp′=Cp or Pr~iCp)

• 作 者: 刘春万 王文亮 李隽
• 机 构: 福建物质结构研究所,延安大学化学系,福建物质结构研究所 福州 350002,延安 716000,福州 350002
• 出 处: 结构化学
• 发表日期: 1992年03期
• 关键词: 簇合物 S Se Te;Cp 分子轨道 键级 桥原子 电子结构 非键轨道

本文用EHMO法对(Mo_4X_4Cp′4](X=0,S,Se,Tc)四个类立方烷型簇合物的电子结构进行了计算,结果表明,桥基X从O到Te,前线区域分子轨道中桥基成分明显增加,能级普遍升高;Mo-Mo间作用有所增强;能隙ΔE(LUMO-HOMO)增大;Mulliken键级P的次序为P_(Mo-Se)>P_(Mo-S)>P_(Mo-Tc)>P_(Mo-o)>P_(Mo-Mo),说明第二过渡系元素Mo更倾向于与较重的se桥结合形成类立方烷型簇合物。

In this paper, the electronic structures of the four quasi-cubic carbohydrate clusters of (Mo_4X_4Cp’4] (X = 0, S, Se, Tc) were calculated by the EHMO method. The results show that the electronic structure of the bridge X from O to Te, In the molecular orbital, the composition of the bridge base is obviously increased, the energy level is generally increased, the interaction between Mo and Mo is enhanced, the energy gap ΔE (LUMO-HOMO) is increased, and the order of Mulliken key P is P_ (Mo-Se)> P_ (Mo-S)> P Mo-Tc> P Mo-o> P Mo-Mo, indicating that the second transition element Mo is more likely to combine with the heavier se bridges to form the stereolithoid clusters Compound.