Photo-epoxidation of α-pinene catalyzed by a MoVI oxo-diperoxo complex modified Ti-based metal-organic framework

Bravo-Sanabria, César A.; Solano-Delgado, Leidy C.; Valdivieso-Zarate, Laura M.; Ospina, Rogelio; Ortega, Fernando Martínez; Ramírez-Caballero, Gustavo E.

doi:10.1016/j.mcat.2023.113240

Cited by 1 publication

(1 citation statement)

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“…The scheme of the photo-stimulated OAT reaction proposed here is indicated similarly by Bravo et al, who observed the Oxygen transfer from the oxo-diperoxomolybdenum complex incorporated into MIL-125-NH 2 . [66] Their work used the MOF type MIL-125-NH 2 (Ti) modified with salicylaldehyde and pyridin-2-aldehyde by a post-synthetic approach to producing Schiff base ligands acting as a support for the oxo-diperoxo molybdenum (MoO(O 2 ) 2 ) complex. The MIL-125-N-O-MoO(O 2 ) 2 and MIL-125-N-N-Mo(O 2 ) 2 catalytic systems performed the photostimulated OAT reaction to selectively form α-pinene oxide.…”

Section: Mofsmentioning

confidence: 99%

Photoinduced Oxygen Atom Transfer to α‐Pinene and R‐Carvone using a Dioxo‐Molybdenum (VI) Complex Incorporated within a Modified UiO‐67 (Zr/Ti) MOF

Valdivieso Zarate,

Bravo Sanabria,

Ramírez Caballero

et al. 2023

Eur J Inorg Chem

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We report a highly selective (100 %) epoxidation of α‐pinene and R‐carvone using an oxygen atom transfer (OAT) reaction facilitated by a dioxo‐Mo complex (Mo(VI)O2Cl2Ln) incorporated into the ligand 5,5’‐dicarboxylate‐2,2’‐bipyridine (bpydc) within a Metal‐Organic Framework (MOF) type UiO‐67. Photo‐stimulated (350 nm) OAT reaction was carried out with oxygen molecular used as the oxidant for 10 h. UiO‐67 was synthesized with a mixture of the ligands 2,2'‐biphenyl‐5,5'‐dicarboxylate (bpdc) and 2,2‐bipyridine‐5,5‐dicarboxylate (bpydc) in different molar ratios (67:33, 50:50, 70:30, 0:100 bpdc:bpydc) to promote a higher presence of catalytic sites, i.e., the dioxo‐Mo complex units. Furthermore, a post‐synthetic exchange of Zr for Ti, between 64:36 to 78:22 Ti:Zr molar ratio, was performed to improve the optical properties of the MOF and promote the photoinduced OAT reaction. The Catalytic system was characterized by FTIR, XRD, 1H NMR, XPS, TGA, N2 adsorption/desorption and UV‐Vis‐DR. The amount of the epoxide monoterpene is proportional to the number of the dioxomolybdenum(VI) units (MoO2) incorporated in the UiO‐67 (Zr/Ti), and the OAT reaction selectivity is due to the absence of the oxygen radicals in the medium of reaction. Besides, The Mo complex exhibited excellent stability after five cycles of use.

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Section: Mofsmentioning

confidence: 99%