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.
引用
收藏
页码：1 / 5
页数：5
相关论文
共 50 条
  • [21] A comparative study of intramolecular hydrogen bond on N-formylformamide derivatives in ground and first singlet excited state: a DFT and TD-DFT study
    Jahani, Peyman Mohammadzadeh
    Jafari, Maedeh
    Kazemian, Mohammad Amin
    SN APPLIED SCIENCES, 2019, 1 (09):
  • [22] DFT study on the ground state and excited state intramolecular proton transfer of propargyl arm containing Schiff bases in solution and gas phases
    Annaraj, B.
    Pan, Sudip
    Neelakantan, M. A.
    Chattaraj, Pratim K.
    COMPUTATIONAL AND THEORETICAL CHEMISTRY, 2014, 1028 : 19 - 26
  • [23] ELECTRON-TRANSFER PROCESSES .33. AN INVERTED REACTIVITY SERIES IN THE REACTION OF TERT-BUTYL RADICAL WITH NUCLEOPHILES
    RUSSELL, GA
    KHANNA, RK
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (05) : 1450 - 1452
  • [24] Theoretical study of hydrogen abstraction from dimethyl ether and methyl tert-butyl ether by hydroxyl radical
    Atadinç, F
    Selçuki, C
    Sari, L
    Aviyente, V
    PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2002, 4 (10) : 1797 - 1806
  • [25] Excited state intramolecular proton transfer in 5-hydroxy flavone: A DFT study
    De, Sankar Prasad
    Ash, Sankarlal
    Bar, Harekrishna
    Bhui, Dipak Kumar
    Dalai, Sudipta
    Misra, Ajay
    JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, 2007, 824 (1-3): : 8 - 14
  • [26] A DFT/TDDFT study of the excited state intramolecular proton transfer based sensing mechanism for the aqueous fluoride chemosensor BTTPB
    Chen, Jun-Sheng
    Zhou, Pan-Wang
    Zhao, Li
    Chu, Tian-Shu
    RSC ADVANCES, 2014, 4 (01): : 254 - 259
  • [27] Photoinduced coupled twisted intramolecular charge transfer and excited-state proton transfer via intermolecular hydrogen bonding: A DFT/TD-DFT study
    Wang, Dandan
    Lu, Rui
    Yuan, Minghu
    Chen, Junsheng
    Feng, Liqiang
    Fu, Aiping
    Tian, Fenghui
    Varandas, Antonio J. C.
    Chu, Tianshu
    CHEMICAL PHYSICS LETTERS, 2014, 610 : 179 - 185
  • [28] Photoinduced coupled twisted intramolecular charge transfer and excited-state proton transfer via intermolecular hydrogen bonding: A DFT/TD-DFT study
    Wang, Dandan
    Lü, Rui
    Yuan, Minghu
    Chen, Junsheng
    Feng, Liqiang
    Fu, Aiping
    Tian, Fenghui
    Varandas, António J.C.
    Chu, Tianshu
    Chemical Physics Letters, 2014, 610-611 : 179 - 185
  • [29] The free radical chemistry of tert-butyl formate:: rate constants for hydroxyl radical, hydrated electron and hydrogen atom reaction in aqueous solution
    Hardison, DR
    Cooper, WJ
    Mezyk, SP
    Bartels, DM
    RADIATION PHYSICS AND CHEMISTRY, 2002, 65 (4-5) : 309 - 315
  • [30] Reaction mechanism of tert-butylation of phenol with tert-butyl alcohol over H-β zeolite: An ONIOM study
    Nie, Xiaowa
    Janik, Michael J.
    Guo, Xinwen
    Liu, Xin
    Song, Chunshan
    CATALYSIS TODAY, 2011, 165 (01) : 120 - 128
12345