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．
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 HPNaF have 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.
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
1998年第4期617-621,共5页
Chemical Journal of Chinese Universities
基金
国家自然科学基金
山东大学跨世纪人才基金
