Effect of 4,4′-dialkyl-2,2′-bipyridine ligands on the hydrolysis of dichlorodioxomolybdenum(VI) catalyst precursors and the switch from homogeneous epoxidation to heterogeneous systems

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• A simple reflux hydrolysis method to prepare MoO 3 /bipyridine hybrid (pre)catalysts. • Structure-directing effect of bipyridine (L) substituents in [MoO 2 Cl 2 (L)] precursors. • The hybrids promoted olefin epoxidation with H 2 O 2 or t -BuOOH as oxidant. • Heterogeneous, reaction-induced self-separating, and homogeneous catalytic features. • Bio-olefins and lignin-based isoeugenol gave useful products, in heterogeneous phase. Molybdenum catalysts have been industrially recognized for decades for liquid phase epoxidation, which is an important chemical reaction process, since epoxides are used for many industrial applications. In this work, molybdenum oxide hybrid catalysts, prepared by a reflux hydrolysis methodology, performed effectively as heterogeneous catalysts or reaction-induced self-separating catalysts under mild reaction conditions; in the two cases, the catalyst separation and reuse are facilitated. Specifically, catalysts with the general formula [MoO 3 (L)], possessing polymeric chain-like (L = 4,4′-dimethyl-2,2′-bipyridine ( 1 )) or oligomeric (L = 4,4′-dinonyl-2,2′-bipyridine ( 2 )) structures comprising corner-sharing {MoO 4 N 2 } units, were synthesized and characterized by various complementary techniques (ATR FT-IR, Raman, 13 C{ 1 H} CP MAS NMR spectroscopy, PXRD, SEM, TGA, elemental analysis, ICP-OES and N 2 sorption isotherms). Small chemical differences in the organic synthesis precursor had important structure directing effects on the type of hybrid material formed. The hybrids promoted olefin epoxidation with H 2 O 2 or tert -butylhydroperoxide (TBHP) as oxidant. For example, 1 catalyzed the conversion of biobased olefins (70 °C) and lignin-based isoeugenol (50 °C) with TBHP to useful bioproducts, in heterogeneous phase, leading to an epoxide yield of 100 % for DL -limonene (3:1 M molar ratio of 1,2-epoxy- p -menth-8-ene to 1,2:8,9-diepoxy- p -menthane), 81 % epoxide yield for fatty acid methyl esters, and 80 % Licarin A selectivity at 40 % isoeugenol conversion. For dienes ( DL -limonene, methyl linoleate), kinetic modelling studies suggested that the formation of the monoepoxides was faster than that of diepoxides, accounting for enhanced monoepoxide selectivity.

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