Abstract
Inspired by the structures of the active site of lactate racemase and H2 activation mechanism of mono-iron hydrogenase, we proposed a series of sulphur–carbon–sulphur (SCS) nickel complexes and computationally predicted their potentials for catalytic hydrogenation of CO2. Density functional theory calculations reveal a metal–ligand cooperated mechanism with the participation of a sulfur atom in the SCS pincer ligand as a proton receiver for the heterolytic cleavage of H2. For all newly proposed complexes containing functional groups with different electron-donating and withdrawing abilities in the SCS ligand, the predicted free energy barriers for the hydrogenation of CO2 to formic acid are in a range of 22.2–25.5 kcal/mol in water. Such a small difference in energy barriers indicates limited contributions of those functional groups to the charge density of the metal center. We further explored the catalytic mechanism of the simplest model complex for hydrogenation of formic acid to formaldehyde and obtained a total free energy barrier of 34.6 kcal/mol for the hydrogenation of CO2 to methanol.
Highlights
Severe climate change is driving people to look for effective ways to reduce the concentration of greenhouse gases, especially carbon dioxide, in the atmosphere [1,2,3]
In Yang and Hall’s hydrogenase catalysis [41], they found the heterolytic cleavage of H2 by Fe and sulfide ligand has a computational study of monoiron hydrogenase catalysis [41], they found the heterolytic cleavage of rather low free energy barrier of 6.6 kcal/mol
Inspired by that the metal center and sulfide ligand may cooperate as an intramolecular frustrated Lewis pair the above findings, we would like to explore the potentials of SCS nickel pincer structures for catalytic (FLP) for H2 activation
Summary
Severe climate change is driving people to look for effective ways to reduce the concentration of greenhouse gases, especially carbon dioxide, in the atmosphere [1,2,3]. In Yang and Hall’s hydrogenase catalysis [41], they found the heterolytic cleavage of H2 by Fe and sulfide ligand has a computational study of monoiron hydrogenase catalysis [41], they found the heterolytic cleavage of rather low free energy barrier of 6.6 kcal/mol. Such results indicate that the metal center and sulfide. Inspired by that the metal center and sulfide ligand may cooperate as an intramolecular frustrated Lewis pair the above findings, we would like to explore the potentials of SCS nickel pincer structures for catalytic (FLP) for H2 activation.
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