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