Mechanism and kinetics of electrocarboxylation of aromatic ketones in ionic liquid Doherty, A. P., Marley, E., Barhdadi, R., Puchelle, V., Wagner, K., & Wallace, G. G. (2018). Mechanism and kinetics of electrocarboxylation of aromatic ketones in ionic liquid. Journal of Electroanalytical Chemistry, 819, 469-473. https://doi.org/10.1016/j.jelechem.2017.12.035 Published in: Journal of Electroanalytical Chemistry Document Version: Peer reviewed version Queen's University Belfast - Research Portal: Link to publication record in Queen's University Belfast Research Portal Publisher rights Copyright 2017 Elsevier. This manuscript is distributed under a Creative Commons Attribution-NonCommercial-NoDerivs License (https://creativecommons.org/licenses/by-nc-nd/4.0/), which permits distribution and reproduction for non-commercial purposes, provided the author and source are cited. General rights Copyright for the publications made accessible via the Queen's University Belfast Research Portal is retained by the author(s) and / or other copyright owners and it is a condition of accessing these publications that users recognise and abide by the legal requirements associated with these rights. Take down policy The Research Portal is Queen's institutional repository that provides access to Queen's research output. Every effort has been made to ensure that content in the Research Portal does not infringe any person's rights, or applicable UK laws. If you discover content in the Research Portal that you believe breaches copyright or violates any law, please contact [email protected]. Download date:01. Apr. 2020
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Mechanism and kinetics of electrocarboxylation of aromatic ketones inionic liquid
Doherty, A. P., Marley, E., Barhdadi, R., Puchelle, V., Wagner, K., & Wallace, G. G. (2018). Mechanism andkinetics of electrocarboxylation of aromatic ketones in ionic liquid. Journal of Electroanalytical Chemistry, 819,469-473. https://doi.org/10.1016/j.jelechem.2017.12.035
Published in:Journal of Electroanalytical Chemistry
Document Version:Peer reviewed version
Queen's University Belfast - Research Portal:Link to publication record in Queen's University Belfast Research Portal
Publisher rightsCopyright 2017 Elsevier.This manuscript is distributed under a Creative Commons Attribution-NonCommercial-NoDerivs License(https://creativecommons.org/licenses/by-nc-nd/4.0/), which permits distribution and reproduction for non-commercial purposes, provided theauthor and source are cited.
General rightsCopyright for the publications made accessible via the Queen's University Belfast Research Portal is retained by the author(s) and / or othercopyright owners and it is a condition of accessing these publications that users recognise and abide by the legal requirements associatedwith these rights.
Take down policyThe Research Portal is Queen's institutional repository that provides access to Queen's research output. Every effort has been made toensure that content in the Research Portal does not infringe any person's rights, or applicable UK laws. If you discover content in theResearch Portal that you believe breaches copyright or violates any law, please contact [email protected].
Mechanism and Kinetics of Electrocarboxylation of Aromatic Ketones in Ionic Liquid Andrew P. Doherty§*, Eunan Marley§, Rachid Barhdadi†, Valentin Puchelle†, Klaudia Wagner¥ and Gordon G Wallace¥
§School of Chemistry and Chemical Engineering, David Keir Building, Queen’s University of Belfast, Stranmillis Road, Belfast, BT9 5AG, United Kingdom. † LEESU (Laboratoire Eau, Environnement et Systèmes Urbains), Université Paris-Est Créteil. Faculté des Sciences et Technologie. 61 avenue du Général de Gaulle, 94010 Créteil Cedex. France ¥ Intelligent Polymer Research Unit, ARC Centre of Excellence for Electromaterials Science, University of Wollongong, Wollongong, NSW, Australia. Abstract
The electrochemical carboxylation of a range of substituted benzophenones was studied in
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Figures
Table 1. List of substituted benzophenones studied, their Hammett substituent constants (), mechanistic and kinetic data. E1/2 is the half-wave potential on the absence of CO2, Ep is the is the first reduction peak potential in the presence of CO2, is potential sweep-rate, K and k2 are the equilibrium and 2nd order rate constants (mol L-1 s-1) for the radical anion-CO2 coupling reaction and k1 is the equivalent 1st order-rate constant (s-1).
Benzophenone E1/2 vs.
Fc/Fc+ Ep / log */ mV log10 K1/2k2 (M-3/2 s-1)§
k1 /s
4-Cyan- 1.0 -1.75 30 3.0 1
BP 0.0 -2.07 32 4.9 (7.10§) 79 (21500§)
3-Methyl -0.07 -2.09 32 5.1 140
4,4-dimethyl -0.34 -2.17 28 5.7 500
4,4-dimethoxy -0.54 -2.27 30 6.0 111
*[25] § [27]
Scheme 1. Possible reaction mechanisms for the ketyl radical electrocarboxylation reaction.
Figure 1. CVs of 1.0 x 10-2 mol L-1 3-methylbenzophenone in [Bmpy] [NTf2] performed at a glassy carbon working electrode at 50 mVs-1, versus ferrocene redox couple, before and after CO2 addition at 1 atm.
Figure 2. Randles-Sevcik plot for the reduction of unsubstituted benzophenone under N2
atmosphere in [Bmpy] [NTf2] at a glassy carbon electrode.
Figure 3. Randles-Sevcik plot for the reduction of unsubstituted benzophenone under CO2 atmosphere (1 atm) in [Bmpy] [NTf2] at a glassy carbon electrode.
Figure 4. A plot of Ep vs. log υ for 4,4-methylbenzophenone.
Figure 5. Apparent rate constant (kapp) vs. Hammett plot for the electrocarboxylation of substituted benzophenons in [Bmpy] [NTf2].