Abstract
High-valent dioxo-Mo species have demonstrated the ability to catalyze industrially interesting alkene-to-epoxide transformations via oxygen atom transfer (OAT) reactions. The impact of electron donor ligands of dioxo-molybdenum complexes [MoO2Ln] covalently supported on TiO2 nanotubes (MoO2Ln/TiO2NT) on OAT to α-pinene, β-pinene, (R)-limonene and camphene has been investigated through the use of UV–vis radiation and molecular oxygen. Molybdenum complexes with electron donor ligands, such as bipyridine, bispyrazole, and terpyridine, exhibited high conversion and selectivity towards epoxide formation. This suggests that electron donation enhances the efficiency of photostimulated OAT. The photonic efficiency (ξ) demonstrates a linear correlation between the ligand structure and the OAT activity, indicating that the electron donation of the ligands enhances electron mobility towards the Mo=O bond. This correlation is evident in the position of the IR and Raman νsym(O=Mo=O) and vasym(O=Mo=O) vibrations of the complex Mo.
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