|
authors |
Neves, P; Nogueira, LS; Gomes, AC; Oliveira, TSM; Lopes, AD; Valente, AA; Goncalves, IS; Pillinger, M |
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nationality |
International |
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journal |
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY |
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author keywords |
Homogeneous catalysis; Epoxidation; Bioolefins; Molybdenum; Nitrogen heterocycles |
|
keywords |
OXO-MOLYBDENUM COMPLEXES; METAL-ORGANIC FRAMEWORK; OLEFIN EPOXIDATION; STRUCTURAL ELUCIDATION; EFFICIENT CATALYSTS; DIOXOMOLYBDENUM(VI)-BIPYRIDINE COMPLEXES; HYDROTHERMAL SYNTHESIS; RHENIUM COMPLEXES; PEROXO COMPLEXES; DIOXO COMPLEXES |
|
abstract |
The chemistry and catalytic performance of the dichlorido complex [MoO2Cl2(pbim)] (1) [pbim = 2-(2-pyridyl)benzimidazole] in the epoxidation of olefins is reported. Complex 1 acts as a precatalyst and is more effective with tert-butyl-hydroperoxide (TBHP) as the oxidant than with aq. hydrogen peroxide: the cis-cyclooctene (Cy) reaction with TBHP gave 98 % epoxide yield at 70 degrees C/24 h. Catalyst characterization showed that 1 is transformed in situ to the oxidodiperoxido complex [MoO(O-2)(2)(pbim)] (2), with H2O2 and a hybrid molybdenum(VI) oxide solid formulated as [MoO3(pbim)] (3) with TBHP. The hybrid material 3 was prepared on a larger scale and explored for the epoxidation of the biorenewable olefins methyl oleate, methyl linoleate, and (R)-(+)-limonene. With TBHP as the oxidant, 3 acts as a source of soluble active species of the type 2. A practical method for recycling oxidodiperoxidomolybdenum(VI) catalysts for the Cy/TBHP reaction is demonstrated by using an ionic liquid as the solvent for the molecular catalyst 2. |
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publisher |
WILEY-V C H VERLAG GMBH |
|
issn |
1434-1948 |
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isbn |
1099-0682 |
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year published |
2017 |
|
issue |
19 |
|
beginning page |
2617 |
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ending page |
2627 |
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digital object identifier (doi) |
10.1002/ejic.201700286 |
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web of science category |
Chemistry, Inorganic & Nuclear |
|
subject category |
Chemistry |
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unique article identifier |
WOS:000403050300012
|
