Trends in Inversion Barriers IV. The Group 15 Analogous of Pyrrole
Trends in Inversion Barriers IV. The Group 15 Analogous of Pyrrole
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反转障碍的趋势 IV。
DOI：
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发表时间：
2002
期刊：
影响因子：
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通讯作者：
P. Schwerdtfeger
中科院分区：
文献类型：
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作者：
S. Pelzer;Karin Wichmann;Ralf Wesendrup;P. Schwerdtfeger
采用从头算和密度泛函方法详细分析了吡咯、磷杂茂、砷杂茂、锑杂茂和双摩尔的反型过程。结果与相应的二乙烯基和二乙基化合物HM（C2 H3）2和HM（C2 H5）2（M = N，P，As，Sb和Bi）进行了比较。反转势垒从第15族元素向下增加，并且从环状化合物经由二乙烯基到二乙基化合物增加。反演过程可以用HOMO/LUMO能量差的二阶Jahn-Teller失真来合理化。B3 LYP计算预测，吡咯环的取代导致四氟和五氟吡咯的非平面结构。
The inversion process of pyrrole, phosphole, arsole, stibole, and bismole is analyzed in detail by using ab initio and density functional techniques. The results are compared with the corresponding divinyl and diethyl compounds, HM(C2H3)2 and HM(C2H5)2, respectively (M = N, P, As, Sb, and Bi). The inversion barrier increases down the Group 15 elements and from the cyclic, via the divinyl to the diethyl compounds. The inversion process can be rationalized in terms of a second-order Jahn−Teller distortion using HOMO/LUMO energy differences. B3LYP calculations predict that fluorination of the pyrrole ring leads to nonplanar structures of both the tetra- and pentafluoropyrrole.