A theoretical study of the electronic effect of the ligand bite angle on the hydrosilylation reaction of ketones by Cu(I) diphosphine complexes |
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Authors: | Thomas Gathy |
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Institution: | Institute of Condensed Matter and Nanosciences, Université Catholique de Louvain, Place Louis Pasteur 1, B-1348 Louvain-la-Neuve, Belgium |
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Abstract: | Diphosphine ligands are commonly used for the catalytic hydrosilylation of ketones using Cu(I) complexes. The electronic effect of the P-Cu-P bite angle has been investigated by a theoretical DFT study. An increase of the P-Cu-P bite angle induces a stronger phosphorus lone pair/Cu-H σ∗ orbital interaction due to a better overlap between these orbitals. This increase in overlap affects structural and electronic properties of the copper hydride catalyst. Increasing the bite angle leads to a decrease of the Cu-P distances and an increases of the Cu-H distances. From an electronic point of view, the effect of an increasing bite angle leads to a weakening of the σ Cu-H orbital, and an increase of the hydride population. The increased polarization of the hydride leads to an easier electron transfer from the σ Cu-H bond to the carbon of the ketone. |
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Keywords: | Diphosphine Cu(I) Bite angle DFT Hydrosilylation Reactivity Catalysis |
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