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Title: Pyrazine-bridged molybdenum(0) carbonyl and molybdenum(VI) oxide network solids as catalysts for epoxidation and sulfoxidation
Author: Gomes, Diana M.
Silva, Andreia F.
Gomes, Ana C.
Neves, Patrícia
Valente, Anabela A.
Gonçalves, Isabel S.
Pillinger, Martyn
Issue Date: Jun-2023
Publisher: Elsevier
Abstract: The horizons of epoxidation and sulfoxidation processes may be expanded by developing new, efficient, and versatile catalysts. In the present work, three pyrazine-bridged molybdenum(0/VI)-based coordination network solids have been investigated for the epoxidation of olefins and the oxidation of sulfides. The materials studied were the Mo0-based metal-organic framework (MOF) fac-Mo(CO)3(pyz)3/2·1/2pyz (1) with a structure consisting of stacked fac-Mo(CO)3(pyz)3/2 coordination layers, the cubic phase fac-Mo(CO)3(pyz)3/2 (2) with a dense framework consisting of two interpenetrating coordination networks, and the molybdenum oxide-pyrazine hybrid material [Mo2O6(pyz)] (3) with a structure consisting of perovskite-like MoO3 layers pillared by pyz molecules. In the model reaction of cis-cyclooctene with tert-butyl hydroperoxide (TBHP) at 70 °C, quantitative yields of the epoxide were obtained within 2 h for 1, 4 h for 2, and 24 h for 3. Catalysts 1-3 were further examined for the epoxidation of other olefins, including the bio-olefins dl-limonene, methyl oleate and methyl linoleate, and the reaction scope was expanded to include the oxidation of sulfides. In the reactions of the bio-olefins, 3 was highly selective, giving only diepoxide and/or monoepoxide products. While the tricarbonyl-pyrazine-molybdenum(0) compounds displayed higher activity, by-products were obtained in the reactions of dl-limonene and methyl linoleate, namely limonene-1,2-diol and hydroxytetrahydrofuran cyclization products, respectively. Catalysts 1-3 displayed high activity for the selective oxidation of sulfides (methyl phenyl sulfide and diphenyl sulfide) to sulfones under mild conditions (35 °C).
Peer review: yes
DOI: 10.1016/j.cattod.2023.114050
ISSN: 0920-5861
Appears in Collections:CICECO - Artigos
DQ - Artigos

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