Room temperature electro-carboxylation of styrene and stilbene derivatives: A comparative study

Alhathlaul, N., Ertekin, Z. , Sproules, S. and Symes, M. D. (2023) Room temperature electro-carboxylation of styrene and stilbene derivatives: A comparative study. Journal of Electroanalytical Chemistry, 950, 117892. (doi: 10.1016/j.jelechem.2023.117892)

Abstract

The use of carbon dioxide as a comparatively cheap, abundant and non-toxic C-1 synthon is a topic of considerable interest and importance. The electrochemical addition of carbon dioxide across carbon–carbon double bonds is one of the more promising of such procedures, offering the possibility to convert a range of alkene substrates to valuable carboxylated products. However, much remains unknown about both the mechanism of reaction and how to influence product specificity during electro-carboxylation of alkenes. Herein, we explore the electrochemical addition of carbon dioxide (1 atm) to a range of olefinic substrates using nickel working electrodes and magnesium anodes at room temperature, producing the mono-substituted carboxylate derivatives preferentially (with no formation of the Markovnikov isomers of these mono-substituted carboxylate derivatives when the starting materials are non-symmetrical). These findings are rationalized using both experimental and computational methods, suggesting that the choice of Ni as a working electrode is critical in determining the reaction outcomes that are observed. Moreover, we also present direct evidence that a pathway whereby the alkene substrates are first reduced at the electrode surface and then react with dissolved CO2 is operating. Together, these results offer the potential for selective access to a range of valuable mono-carboxylic acids via the reduction of the corresponding alkene precursors in the presence of carbon dioxide.

• Item Type: Articles
• Additional Information: This work was supported by the EPSRC (EP/W033135/1). NA thanks her sponsors (Jouf University, the Royal Embassy of Saudi Arabia Cultural Bureau, and the Ministry of Education in Saudi Arabia) for their financial support. ZE thanks the Scientific and Technological Research Council of Turkey (grant number: TUBITAK 2219) for a postdoctoral fellowship. MDS thanks the Royal Society for a University Research Fellowship (URF\R\211007).
• Keywords: Electrochemical carbon dioxide reduction; electrocatalysis; styrene; stilbene; carboxylation.
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Sproules, Dr Stephen and Symes, Professor Mark and Alhathlaul, Nada Warid A and Ertekin, Dr Zeliha

Creator Roles

Alhathlaul, N. W. A.: Methodology, Data curation, Investigation
Ertekin, Z.: Investigation
Sproules, S.: Investigation, Writing – review and editing
Symes, M.: Conceptualization, Supervision, Writing – review and editing

• Authors: Alhathlaul, N., Ertekin, Z., Sproules, S., and Symes, M. D.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Journal of Electroanalytical Chemistry
• Publisher: Elsevier
• ISSN: 1572-6657
• Published Online: 29 October 2023
• Copyright Holders: Copyright: © 2023 The Author(s)
• First Published: First published in Journal of Electroanalytical Chemistry 950: 117892
• Publisher Policy: Reproduced under a Creative Commons licence
• Data DOI: 10.5525/gla.researchdata.1520

Project Code	Award No	Project Name	Principal Investigator	Funder's Name	Funder Ref	Lead Dept
316623		Decoupled Electrolysis for the Production of Zero-Carbon Hydrogen	Mark Symes	Engineering and Physical Sciences Research Council (EPSRC)	EP/W033135/1	Chemistry
312636		Driving energetically uphill processes using metal-ligand coordination complexes - Renewal	Mark Symes	The Royal Society (ROYSOC)	URF\R\211007	Chemistry