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The Dual Roles of Phenylenediamines: Using their Voltammetric Behavior to Measure the Hydrogen Donor and Acceptor Abilities of Alcohols in Acetonitrile
Author(s) -
Tessensohn Malcolm E.,
Lim Sihao,
Koh Yu Rong,
Hirao Hajime,
Webster Richard D.
Publication year - 2017
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201700976
Subject(s) - acetonitrile , chemistry , cyclic voltammetry , acceptor , hydrogen bond , electrochemistry , hydrogen , photochemistry , proton , voltammetry , inorganic chemistry , medicinal chemistry , molecule , organic chemistry , electrode , physics , quantum mechanics , condensed matter physics
Cyclic voltammetry experiments on 2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (P) in acetonitrile in the presence of varying concentrations of alcohols indicate that the oxidized forms of the compound (P .+ and P 2+ ) interact with the alcohols through a hydrogen‐bonding mechanism where P .+ and P 2+ act as the hydrogen donor and the alcohols act as acceptors. However, the neutral form (P) largely acts as a hydrogen acceptor but only for strong hydrogen donors that do not undergo proton‐transfer reactions with the phenylenediamine. These results were ascertained based on measuring the difference in potential of the two one‐electron transfer reactions (Δ E P ox(1, 2) =| E P ox(1) − E P ox(2) |) in the oxidative electrochemistry of P, which thereby allows a simple measure of relative hydrogen bonding strengths.