The imino pyridine Schiff base cobalt(II) and nickel(II) complexes (C1 and C2) and their functionalised γ-Fe₃O₄ counterparts (Fe₃O₄@C1 and Fe₃O₄@C2) were synthesised and characterised using IR, elemental analysis, and ESI-MS for C1 and C2, and single crystal X-ray diffraction for C1, while the functionalised materials Fe₃O₄@C1 and Fe₃O₄@C2 were characterized using IR, XRD, SEM, TEM, EDS, ICP-OES, XPS and TGA. Complexes C1, C2 and the functionalised materials Fe₃O₄@C1 and Fe₃O₄@C2 were tested as catalysts for the selective transfer hydrogenation of cinnamaldehyde and all four pre-catalysts showed excellent catalytic activity. Complexes C1 and C2 acted as homogeneous catalysts with high selectivity towards the formation of hydrocinnamaldehyde (88.7% and 92.6%, respectively) while Fe₃O₄@C1 and Fe₃O₄@C2 acted as heterogeneous catalysts with high selectivity towards cinnamyl alcohol (89.7% and 87.7%, respectively). Through in silico studies of the adsorption energies, we were able to account for the different products formed using the homogeneous and the heterogeneous catalysts which we attribute to the preferred interaction of the C=C moiety in the substrate with the Ni centre in C2 (−0.79 eV) rather than the C=O (−0.58 eV).

Keywords: Fe₃O₄-immobilised pre-catalysts; transfer hydrogenation; cinnamaldehyde

Projects

Currently no objects available

Currently no objects available