DFT and experimental analysis of aluminium chloride as a Lewis acid proton carrier catalyst for dimethyl carbonate carboxymethylation of alcohols

Saimeng Jin; Yin Tian; Con Robert McElroy; Dongqi Wang; James H. Clark; Andrew J. Hunt

doi:10.1039/C7CY01190C

DFT and experimental analysis of aluminium chloride as a Lewis acid proton carrier catalyst for dimethyl carbonate carboxymethylation of alcohols

Saimeng Jin, Yin Tian^*, Con Robert McElroy, Dongqi Wang, James H. Clark, Andrew J. Hunt

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	4859-4865
Number of pages	7
Journal	Catalysis Science and Technology
Volume	7
Issue number	20
DOIs	https://doi.org/10.1039/C7CY01190C https://doi.org/10.1039/c7cy01190c
Publication status	Published - 28 Sept 2017

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© 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

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title = "DFT and experimental analysis of aluminium chloride as a Lewis acid proton carrier catalyst for dimethyl carbonate carboxymethylation of alcohols",

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.",

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T1 - DFT and experimental analysis of aluminium chloride as a Lewis acid proton carrier catalyst for dimethyl carbonate carboxymethylation of alcohols

AU - Jin, Saimeng

AU - Tian, Yin

AU - McElroy, Con Robert

AU - Wang, Dongqi

AU - Clark, James H.

AU - Hunt, Andrew J.

N1 - © 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

PY - 2017/9/28

Y1 - 2017/9/28

N2 - 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.

AB - 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.

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JO - Catalysis Science and Technology

JF - Catalysis Science and Technology

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ER -

DFT and experimental analysis of aluminium chloride as a Lewis acid proton carrier catalyst for dimethyl carbonate carboxymethylation of alcohols

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