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

Shahbaz Ahmad; Elizabeth Berry; Conor Boyle; Christopher Hudson; Oliver W. Ireland; Emily A. Thompson; Michael Buehl

doi:10.1007/s00894-018-3915-1

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

Shahbaz Ahmad, Elizabeth Berry, Conor Boyle, Christopher Hudson, Oliver W. Ireland, Emily A. Thompson, Michael Buehl

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

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., L_nM(CO) + OH⁻ → [L_nM(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.

Original language	English
Article number	45
Number of pages	8
Journal	Journal of Molecular Modeling
Volume	25
Early online date	25 Jan 2019
DOIs	https://doi.org/10.1007/s00894-018-3915-1
Publication status	Published - Feb 2019

Keywords

Homogeneous catalysis
Water gas shift reaction
Hieber base reaction
Density functional theory

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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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@article{375c7a5a0def46c3b1619e8a959c00ca,

title = "Formation of metallacarboxylic acids through Hieber base reaction. A density functional theory study",

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.",

keywords = "Homogeneous catalysis, Water gas shift reaction, Hieber base reaction, Density functional theory",

author = "Shahbaz Ahmad and Elizabeth Berry and Conor Boyle and Christopher Hudson and Ireland, {Oliver W.} and Thompson, {Emily A.} and Michael Buehl",

note = "We thank EaStCHEM and the School of Chemistry for support.",

year = "2019",

month = feb,

doi = "10.1007/s00894-018-3915-1",

language = "English",

volume = "25",

journal = "Journal of Molecular Modeling",

issn = "1610-2940",

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TY - JOUR

T1 - Formation of metallacarboxylic acids through Hieber base reaction. A density functional theory study

AU - Ahmad, Shahbaz

AU - Berry, Elizabeth

AU - Boyle, Conor

AU - Hudson, Christopher

AU - Ireland, Oliver W.

AU - Thompson, Emily A.

AU - Buehl, Michael

N1 - We thank EaStCHEM and the School of Chemistry for support.

PY - 2019/2

Y1 - 2019/2

N2 - 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.

AB - 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.

KW - Homogeneous catalysis

KW - Water gas shift reaction

KW - Hieber base reaction

KW - Density functional theory

U2 - 10.1007/s00894-018-3915-1

DO - 10.1007/s00894-018-3915-1

M3 - Article

SN - 1610-2940

VL - 25

JO - Journal of Molecular Modeling

JF - Journal of Molecular Modeling

M1 - 45

ER -

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

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