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Aliphatic Mn–PNP complexes for the CO2 hydrogenation reaction: a base free mechanism

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Abstract

Using density functional theory (DFT) calculations, a series of aliphatic amido Mn–PNP-based complexes was studied for base free CO2 hydrogenation. The amido group present in the aliphatic PNP ligand favours a heterolytic H2 cleavage and proton transfer mechanism contrary to any active catalyst for CO2 hydrogenation, where base facilitates this process. Further, a set of σ-donor (PH3 and PMe3) and π-acceptor (CO and PF3) ligand-based Mn–PNP complexes was studied to understand the electronic and steric effects on the rate determining steps. Our reaction free-energy profile suggests that Mn1 is a promising base-free catalyst for CO2 hydrogenation with an overall free energy barrier of 23.3 kcal mol−1. We found that the proper combination of σ-donor and π-acceptor ligands may not be a necessary criteria to improve the overall activity of the catalyst although π-acceptor ligands favour heterolytic H2-cleavege and σ-donor ligands favour the hydride transfer mechanism.

Graphical abstract: Aliphatic Mn–PNP complexes for the CO2 hydrogenation reaction: a base free mechanism

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Publication details

The article was received on 14 Apr 2017, accepted on 25 May 2017 and first published on 26 May 2017


Article type: Paper
DOI: 10.1039/C7CY00737J
Citation: Catal. Sci. Technol., 2017, Advance Article
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    Aliphatic Mn–PNP complexes for the CO2 hydrogenation reaction: a base free mechanism

    K. S. Rawat and B. Pathak, Catal. Sci. Technol., 2017, Advance Article , DOI: 10.1039/C7CY00737J

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