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., LM(CO) + OH → [LM(COH)], M = Fe, Ru, Os, L = CO, PMe, PF, 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. Graphical abstract ᅟ.

Download full-text PDF

Source
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6347588PMC
http://dx.doi.org/10.1007/s00894-018-3915-1DOI Listing

Publication Analysis

Top Keywords

hieber base
8
base reaction
8
density functional
8
functional theory
8
formation metallacarboxylic
4
metallacarboxylic acids
4
acids hieber
4
reaction density
4
theory study
4
study density
4

Similar Publications

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!