On the structure of phenonium ions:: The important role of back-bonding interaction in carbocation chemistry

被引:27
作者
del Río, E [1 ]
Menéndez, MI [1 ]
López, R [1 ]
Sordo, TL [1 ]
机构
[1] Univ Oviedo, Fac Quim, Dept Quim Fis & Analit, E-33006 Oviedo, Asturias, Spain
关键词
D O I
10.1021/jp994068g
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Binding in phenonium ions [C6H5-C-2(OH)(4)](+), [C6H5-C-2(CH3)(4)](+), [C6H5-C2F4](+), [p-NC-C6H4-C2H4](+), [p-OHC-C6H4-C2H4](+), [C6H5-C2H4](+), [p-F-C6H4-C2H4](+), [p-H3C-C6H4-C2H4](+) [p-HO-C6H4-C2H4](+), [C6H5-C-2(CHO)(4)](+), and [C6H5-C-2(CN)(4)](+) was investigated with the B3LYP/6-31G* method. The analysis of the Kohn-Sham orbitals and a Bader analysis of the computed electron density of the phenonium ion, [C6H5-C2H4](+), clearly show that back-bonding from the phenyl cation moiety to the ethylene fragment determines the formation of the three-membered cycle, rendering the shielding of the ipso carbon atom similar to that for an sp(3) C, while an extension of the conjugation occurs as both pi systems merge with each other. The important stabilization gained from this process determines the orthogonal conformation of the phenonium ion.
引用
收藏
页码:5568 / 5571
页数:4
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