Photo-assisted selective oxidation of monoterpenes by a covalently supported dioxo-molybdenum complex on TiO2 : Effect of electron donor ligands

被引：2
作者：
Martinez, Henry [1 ]
Amaya, Alvaro A. [2 ]
Paez-Mozo, Edgar [1 ]
Martinez, O. Fernando [1 ]
机构：
[1] Univ Ind Santander, Escuela Quim, Ctr Invest Catalisis CICAT, Km 2 Via El Refugio, Piedecuesta, Santander, Colombia
[2] Univ Santander, Fac Ciencias Exactas Nat & Agr, Ciencias Basicas & Aplicadas Sostenibilidad CIBAS, Bucaramanga, Colombia
来源：
MOLECULAR CATALYSIS | 2024年 / 565卷
关键词：
Monoterpenes; Selective oxidation; Photocatalysis; Oxygen activation; Dioxo-Mo complexes; OXYGEN-ATOM-TRANSFER; SCHIFF-BASE LIGANDS; TRANSFER REACTIVITY; MOLECULAR-OXYGEN; MO-95; NMR; DIOXOMOLYBDENUM(VI) COMPLEXES; CATALYTIC-ACTIVITY; ALPHA-PINENE; OLEFIN EPOXIDATION; AEROBIC OXIDATION;
D O I：
10.1016/j.mcat.2024.114358
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
High-valent dioxo-Mo species have demonstrated the ability to catalyze industrially interesting alkene-toepoxide transformations via oxygen atom transfer (OAT) reactions. The impact of electron donor ligands of dioxo-molybdenum complexes [MoO 2 Ln] covalently supported on TiO 2 nanotubes (MoO 2 Ln/TiO 2 - NT) on OAT to alpha-pinene, beta-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 ( xi) 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 nu sym (O =Mo =O) and v asym (O =Mo =O) vibrations of the complex Mo.
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页数：13
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