Jin, Saimeng, Tian, Yin, McElroy, Con Robert orcid.org/0000-0003-2315-8153 et al. (3 more authors) (2017) DFT and experimental analysis of aluminium chloride as a Lewis acid proton carrier catalyst for dimethyl carbonate carboxymethylation of alcohols. Catalysis Science and Technology. pp. 4859-4865. ISSN 2044-4761
Abstract
The Lewis acid catalysed mechanism of dimethyl carbonate (DMC) mediated carboxymethylation of alcohol was investigated experimentally and through computational chemistry methods including density functional theory (DFT). Experimental data showed that catalytic loading of AlCl3 enabled the quantitative carboxymethylation of octanol in less than 20 h, while in the absence of a catalyst only trace product was observed. The geometry of the identified transition states and related energy barriers indicate that the activation energies in AlCl3 catalysed pathways are significantly lower than those in catalyst-free pathways. Theoretical quantum chemistry methods were utilised to explore and analyse the complex of DMC with AlCl3. Natural bond orbital theory analysis and molecular orbital analysis demonstrated that the dipole present in Al-Cl covalent bonding plays a vital role in assisting the proton-transfer process. Most importantly, the reaction mechanism disclosed in this research can aid in the exploration of new Lewis acid catalysed processes in the field of dialkyl carbonate chemistry.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © The Royal Society of Chemistry 2017. This is an author-produced version of a paper accepted for publication. Uploaded with permission of the publisher/copyright holder. Further copying may not be permitted; contact the publisher for details |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York The University of York > Faculty of Sciences (York) > Chemistry (York) |
Depositing User: | Pure (York) |
Date Deposited: | 04 Oct 2017 09:00 |
Last Modified: | 04 Jan 2025 00:12 |
Published Version: | https://doi.org/10.1039/C7CY01190C |
Status: | Published |
Refereed: | Yes |
Identification Number: | 10.1039/C7CY01190C |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:122023 |