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Formation of metallacarboxylic acids through Hieber base reaction. A density functional theory study

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Ahmad_2019_JMM_Formation_CC.pdf (1.439Mb)
Date
02/2019
Author
Ahmad, Shahbaz
Berry, Elizabeth
Boyle, Conor
Hudson, Christopher
Ireland, Oliver W.
Thompson, Emily A.
Buehl, Michael
Keywords
Homogeneous catalysis
Water gas shift reaction
Hieber base reaction
Density functional theory
QD Chemistry
NDAS
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Abstract
Using density functional theory (B97-D/ECP2/PCM//RI-BP86/ECP1 level), we have studied the effects of ligand variation on OH− uptake by transition-metal carbonyls (Hieber base reaction), i.e., LnM(CO) + OH− → [LnM(CO2H)]−, M = Fe, Ru, Os, L = CO, PMe3, PF3, py, bipy, Cl, H. The viability of this step depends notably on the nature of the co-ligands, and a large span of driving forces is predicted, ranging from ΔG = −144 kJ/mol to +122 kJ/mol. Based on evaluation of atomic charges from natural population analysis, it is the ability of the co-ligands to delocalize the additional negative charge (through their π-acidity) that is the key factor affecting the driving force for OH− uptake. Implications for the design of new catalysts for water gas shift reaction are discussed.
Citation
Ahmad , S , Berry , E , Boyle , C , Hudson , C , Ireland , O W , Thompson , E A & Buehl , M 2019 , ' Formation of metallacarboxylic acids through Hieber base reaction. A density functional theory study ' , Journal of Molecular Modeling , vol. 25 , 45 . https://doi.org/10.1007/s00894-018-3915-1
Publication
Journal of Molecular Modeling
Status
Peer reviewed
DOI
https://doi.org/10.1007/s00894-018-3915-1
ISSN
1610-2940
Type
Journal article
Rights
Copyright © The Author(s) 2019. Open Access. This article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.
Description
We thank EaStCHEM and the School of Chemistry for support.
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  • University of St Andrews Research
URI
http://hdl.handle.net/10023/16940

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