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.
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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6347588 | PMC |
http://dx.doi.org/10.1007/s00894-018-3915-1 | DOI Listing |
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