Investigation on PCET-accompanied Dimerization of 5-hydroxy-1, 4-naphthoquinone in the Process of Electrochemical Reduction by In Situ FT-IR Spectroelectrochemistry and Density Functional Calculation
被引:15
作者:
Li, Dan
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h-index: 0
机构:
Anhui Univ, Dept Chem, Hefei 230039, Peoples R ChinaAnhui Univ, Dept Chem, Hefei 230039, Peoples R China
Li, Dan
[1
]
Cheng, Longjiu
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机构:
Anhui Univ, Dept Chem, Hefei 230039, Peoples R ChinaAnhui Univ, Dept Chem, Hefei 230039, Peoples R China
Cheng, Longjiu
[1
]
Jin, Baokang
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h-index: 0
机构:
Anhui Univ, Dept Chem, Hefei 230039, Peoples R ChinaAnhui Univ, Dept Chem, Hefei 230039, Peoples R China
Jin, Baokang
[1
]
机构:
[1] Anhui Univ, Dept Chem, Hefei 230039, Peoples R China
dimerization;
proton coupled electron transfers (PCET);
5-hydroxy-1;
4-naphthoquinone;
hydrogen-bonding;
in situ FT-IR spectroelectrochemistry;
density functional calculation;
COUPLED ELECTRON-TRANSFER;
CYCLIC VOLTABSORPTOMETRY;
REVERSIBLE DIMERIZATION;
PROTON-TRANSFER;
ANION-RADICALS;
BENZOQUINONE;
TRANSFERS;
QUINONES;
COMPLEX;
DIMER;
D O I:
10.1016/j.electacta.2014.03.049
中图分类号:
O646 [电化学、电解、磁化学];
学科分类号:
081704 ;
摘要:
Electron transfers (ET) of 5-hydroxy-1, 4-naphthoquinone (HNQ) and 5-hydroxy-2-methyl-1, 4-naphthoquinone (HMeNQ) have been investigated in acetonitrile and proton donors mixed media. Although there is merely a small difference in structure between HMeNQ having a methyl, and HNQ not having a methyl, the reduction of HNQ involves proton coupled electron transfers (PCET) process while HMeNQnot. Both CV and rapid-scan IR spectra support the existence of intermediate HNQ and dimer in acetonitrile during electrochemical reduction. Density functional calculations show that proton transfers (PT) occur when forming dimer, indicating that HNQ has PCET-accompanied dimerization mechanism. Besides, dimer also undergoes two successive ET processes to form quinone. When proton donors are added to HNQ dimerization is inhibited owing to intermolecular hydrogen-bonding, accompanying by the interruption of PCET process. (C) 2014 Elsevier Ltd. All rights reserved.
机构:
Univ Paris 07, CNRS, Unite Mixte Rech Univ 7591, Electrochim Mol Lab, F-75251 Paris 05, FranceUniv Paris 07, CNRS, Unite Mixte Rech Univ 7591, Electrochim Mol Lab, F-75251 Paris 05, France
机构:
Univ Paris 07, CNRS, Unite Mixte Rech Univ 7591, Electrochim Mol Lab, F-75251 Paris 05, FranceUniv Paris 07, CNRS, Unite Mixte Rech Univ 7591, Electrochim Mol Lab, F-75251 Paris 05, France