کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
192202 | 459737 | 2010 | 10 صفحه PDF | دانلود رایگان |
This report seeks to address the role of hydrogen bonding with Brønsted acids and bases in proton-coupled electron transfer (PCET) as it pertains to concerted or stepwise pathways of quinone (Q) and hydroquinone (QH2) electrochemistry. This study was performed using a series of techniques that included cyclic voltammetry (CV), digital simulations, computational chemistry and 1H NMR. Hydrogen bonding was inferred by a decrease in diffusion coefficient (D) values measured using a pulsed gradient echo- (PGE-) 1H NMR technique. Changes of 40.8% and 37.9% in D values were only noted after the addition of two equivalents of acetate to 1,4-hydroquinone (1,4-QH2) and catechol (1,2-QH2), respectively. In contrast, the D values for the addition of selected amines (pyridine, N,N-diisopropylethylamine and triethylamine) changed only 3.2% on average. Quantum mechanical calculations were conducted to determine the pKa of all quinoid species to serve as a starting point for the determination of equilibrium constants in voltammetric simulations. Simulations indicate that 1,4-benzoquinone undergoes stepwise electron–proton transfer upon addition of acetic acid, N-ethyldiisopropylammonium perchlorate and pyridinium nitrate and were simulated without the presence of hydrogen bonds. The QH2 compounds show stepwise proton–electron transfers after addition of the both the conjugate amines and acetate.
Journal: Electrochimica Acta - Volume 55, Issue 22, 1 September 2010, Pages 6507–6516