Heterogenised catalysts for the H-transfer reduction reaction of aldehydes: influence of solvent and solvation effects on reaction performances

Heterogenisation of homogeneous catalysts onto solid supports represents a potential strategy to make the homogeneous catalytic function recyclable and reuseable. Yet, it is usually the case that immobilised catalysts have much lower catalytic activity than their homogeneous counterpart. In addition, the presence of a solid interface introduces a higher degree of complexity by modulating solid/fluid interactions, which can often influence adsorption properties of solvents and reactive species and, ultimately, catalytic activity. In this work, the influence of support and solvent in the H-transfer reduction of propionaldehyde over Al((OPr)-Pr-i)(3)-SiO2, Al((OPr)-Pr-i)(3)-TiO2 and Al((OPr)-Pr-i)(3)-Al2O3 heterogenised catalysts has been studied. Reaction studies are coupled with both NMR relaxation measurements as well as molecular dynamics (MD) simulations in order to unravel surface and solvation effects during the reaction. The results show that, whilst the choice of the support does not influence significantly catalytic activity, reactions carried out in solvents with high affinity for the catalyst surface, or able to hinder access to active sites due to solvation effects, have a lower activity. MD calculations provide key insights into bulk solvation effects involved in such reactions, which are thought to play an important role in determining the catalytic behaviour. The activity of the heterogenised catalysts was found to be comparable with that of the homogeneous Al((OPr)-Pr-i)(3) catalysts for all supports used, showing that for the type of reaction studied immobilisation of the homogeneous catalyst onto solid supports is a viable, robust and effective strategy.

Automated summary

Heterogenisation of homogeneous catalysts onto solid supports is a potential strategy for recyclable and reuseable catalysis. However, immobilised catalysts usually exhibit lower activity compared to their homogeneous counterparts. In this study, the influence of support and solvent on the catalytic activity of heterogenised catalysts in the H-transfer reduction of propionaldehyde was investigated. The results showed that the choice of support does not significantly affect catalytic activity, but solvents with high affinity for the catalyst surface or solvation effects that hinder access to active sites result in lower activity. Molecular dynamics simulations provided insights into the solvation effects involved in the reactions, which play a crucial role in determining the catalytic behavior. The activity of the heterogenised catalysts was found to be comparable to the homogeneous catalysts, indicating that immobilisation of the homogeneous catalyst onto solid supports is a viable and effective strategy for this type of reaction.