Formation of metallacarboxylic acids through Hieber base reaction. A density functional theory study
Date
02/2019Author
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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
ISSN
1610-2940Type
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.
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We thank EaStCHEM and the School of Chemistry for support.Collections
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