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 [1 ]
Cheng, Longjiu [1 ]
Jin, Baokang [1 ]
机构
[1] Anhui Univ, Dept Chem, Hefei 230039, Peoples R China
关键词
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.
引用
收藏
页码:387 / 396
页数:10
相关论文
共 32 条
[1]   Acid/base and hydrogen bonding effects on the proton-coupled electron transfer of quinones and hydroquinones in acetonitrile: Mechanistic investigation by voltammetry, 1H NMR and computation [J].
Alligrant, Timothy M. ;
Hackett, John C. ;
Alvarez, Julio C. .
ELECTROCHIMICA ACTA, 2010, 55 (22) :6507-6516
[2]   The stabilizing role of intramolecular hydrogen bonding in disubstituted hydroxy-quinones [J].
Armendariz-Vidales, Georgina ;
Martinez-Gonzalez, Eduardo ;
Javier Cuevas-Fernandez, Hector ;
Omar Fernandez-Campos, Didier ;
Burgos-Castillo, Rutely C. ;
Frontana, Carlos .
ELECTROCHIMICA ACTA, 2013, 110 :628-633
[3]   Electrochemical and chemical formation of a low-barrier proton transfer complex between the quinone dianion and hydroquinone [J].
Astudillo, Pablo D. ;
Valencia, Drochss P. ;
Gonzalez-Fuentes, Miguel A. ;
Diaz-Sanchez, Blanca R. ;
Frontana, Carlos ;
Gonzalez, Felipe J. .
ELECTROCHIMICA ACTA, 2012, 81 :197-204
[4]   Proton-coupled electron transfer of flavodoxin immobilized on nanostructured tin dioxide electrodes: Thermodynamics versus kinetics control of protein redox function [J].
Astuti, Y ;
Topoglidis, E ;
Briscoe, PB ;
Fantuzzi, A ;
Gilardi, G ;
Durrant, JR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (25) :8001-8009
[5]   Investigation on the π-Dimer/σ-Dimer of 1,8-Dihydroxy-9,10-anthracenedione in the Process of Electrochemical Reduction by Using IR Spectroelectrochemical Cyclic Voltabsorptometry and Derivative Cyclic Voltabsorptometry [J].
Cheng, Wang-Xing ;
Jin, Bao-Kang ;
Huang, Peng ;
Cheng, Long-jiu ;
Zhang, Sheng-Yi ;
Tian, Yu-Peng .
JOURNAL OF PHYSICAL CHEMISTRY C, 2013, 117 (08) :3940-3948
[6]   The Effect of H-Bonding and Proton Transfer on the Voltammetry of 2,3,5,6-Tetramethyl-p-phenylenediamine in Acetonitrile. An Unexpectedly Complex Mechanism for a Simple Redox Couple [J].
Clare, Laurie A. ;
Rojas-Sligh, Lydia E. ;
Maciejewski, Sonia M. ;
Kangas, Karina ;
Woods, Jessica E. ;
Deiner, L. Jay ;
Cooksy, Andrew ;
Smith, Diane K. .
JOURNAL OF PHYSICAL CHEMISTRY C, 2010, 114 (19) :8938-8949
[7]   Electrochemical and homogeneous proton-coupled electron transfers:: Concerted pathways in the one-electron oxidation of a phenol coupled with an intramolecular amine-driven proton transfer [J].
Costentin, C ;
Robert, M ;
Savéant, JM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (14) :4552-4553
[8]   Electrochemical approach to the mechanistic study of proton-coupled electron transfer [J].
Costentin, Cyrille .
CHEMICAL REVIEWS, 2008, 108 (07) :2145-2179
[9]  
Frisch M. J., 2016, Gaussian 03 Revision B.03
[10]   Hydrogen-bonding and protonation effects in electrochemistry of quinones in aprotic solvents [J].
Gupta, N ;
Linschitz, H .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (27) :6384-6391