高等学校化学学报 ›› 1998, Vol. 19 ›› Issue (4): 617.

• 论文 • 上一篇    下一篇

HPXF(X=Li,Na)的构型及反应性能的从头算研究

卢秀慧1, 王沂轩2, 邓从豪2   

  1. 1. 济南大学化学系, 济南, 250002;
    2. 山东大学化学院, 济南, 250100
  • 收稿日期:1996-11-12 出版日期:1998-04-24 发布日期:1998-04-24
  • 通讯作者: 王沂轩
  • 作者简介:卢秀慧,男,40岁,副教授.
  • 基金资助:

    国家自然科学基金;山东大学跨世纪人才基金

Ab Initio Study on the Geometries and Reaction Activities of HPXF(X=Li, Na)

LU Xiu-Hui1, WANG Yi-Xuan2, DENG Cong-Hao2   

  1. 1. Chemistry Department of Jinan University, Jinan, 250002;
    2. Institute of Chemistry of Shandong University, Jinan, 250100
  • Received:1996-11-12 Online:1998-04-24 Published:1998-04-24

摘要: 用RHF/6-31G*从头算解析梯度法优化了类磷烯HPXF(X=Li,Na)的平衡构型,分析了各构型的结构特点及稳定性.通过与磷烯(1HP)相比较,探讨了HPXF(X=Li,Na)的反应活性,还简单讨论了碱金属原子对HPXF(X=Li,Na)三元环构型稳定性和反应活性的影响.结果表明,HPLiF和HPNaF均具有3种平衡构型,其中三元环构型最稳定,也是参加反应的基本构型:类磷烯与相应的1HP相比,可成为一种使反应容易控制、选择性好和易获得的亲电反应中间体.

关键词: 磷烯, 反应活性, 从头算

Abstract: The Geometries of the two lacking electron fragments HPXF(X=Li, Na) have been investigated by using ab initio method at RHF/6-31G* level, and characteristics of all the geometries have also been analysed in terms of bonding concepts. By comparing with free phosphinidene ( 1HP), reaction activities of HPXF(X=Li, Na) were discussed. Moreover, the effect of alkali metal atoms on the geometries and activities of HPXF(X=Li, Na) have been briefly discussed.The results indicate that both HPLiF and HPNaFhave three types of equilibrium geometries among them, the three-membered ring geometry is the most stable one, and it may be the basic geometry taking part in chemical reactions. It is expected that HPXF(X=Li, Na) is a superior electrophilic intermediate to free phosphinidene in selectivity and control ability.

Key words: Phosphinidene, Reaction activity, Ab initio

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