Mechanism of the intramolecular hydrogen transfer reaction at ground and excited state of tert-butyl radical: An ESR and DFT study

被引：0
|
作者：
Takada, Tomoya [2 ]
Kawabata, Hiroshi [3 ]
Tachikawa, Hiroto [1 ]
机构：
[1] Hokkaido Univ, Grad Sch Engn, Div Mat Chem, Kita Ku, Sapporo, Hokkaido 0608628, Japan
[2] Asahikawa Natl Coll Technol, Dept Mat Chem, Asahikawa, Hokkaido 0718142, Japan
[3] Kyoto Univ, Venture Business Lab, Sakyo Ku, Kyoto 6068501, Japan
来源：
JOURNAL OF MOLECULAR STRUCTURE | 2012年 / 1020卷
基金：
日本学术振兴会;
关键词：
ESR; DFT; Radical; Hydrogen transfer; Photoreaction; PHOTOINDUCED ISOMERIZATION; ALKYL RADICALS; ELECTRON-CAPTURE;
D O I：
10.1016/j.molstruc.2012.04.005
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：
Hydrogen transfer reactions at the ground and excited states of tert-butyl radical to form iso-butyl radical have been investigated by means of ab initio calculation and electron spin resonance (ESR) spectroscopy. It was found that tert-butyl radical irradiated with 254 nm ultraviolet light converts quite efficiently to iso-butyl radical. Also, it was suggested that this conversion occurs as an intramolecular hydrogen transfer from a methyl group of tert-butyl radical to a radical site (central carbon atom). The theoretical calculations showed that barrier height of hydrogen transfer at the excited state is significantly lower than that of ground state. The mechanism of internal hydrogen atom conversion from tert-butyl to iso-butyl radicals was discussed. (C) 2012 Elsevier B.V. All rights reserved.
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页数：5
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