Synthesis, Characterization, and Catalytic Behavior of Dioxomolybdenum Complexes Bearing AcAc-Type Ligands

A series of [MoO2(acac′)2] [acac′ = acetylacetonato‐type ligand: dibenzoylmethane (3), 1‐benzoylacetone (4), bis(p‐methoxybenzoyl)methane (5), 2‐acetylcyclopentanone (6), 2‐acetylcyclohexanone (7), and 2‐acetyl‐1‐tetralone (8)] complexes have been synthesized in yields of 44–83 % by a simple synthetic method by using sodium molybdate and the desired acac‐type ligand as starting materials. All the complexes were characterized by IR, UV/Vis, NMR, and high‐resolution ESI‐MS, and for compounds 3, 4, and 8, solid‐state structures were obtained by X‐ray diffraction. All the complexes contain a cis‐dioxomolybdenum moiety, as proven by the characteristic Mo=O vibrations in the IR spectra and the occurrence of four sets of signals in the NMR spectra of the complexes bearing asymmetrical ligands (4 and 6–8), and confirmed by the solid‐state structures. The complexes were found to be active as catalysts in the dehydration of 1‐phenylethanol to styrene using technical‐grade toluene as the solvent in air at 100 °C. The highest catalytic activity was found for [MoO2{(tBuCO)2CH}2] (2), followed by [MoO2{(C6H5CO)2CH}2] (3). Both complexes were also found to be active in the dehydration of other alcohols, including allylic, aliphatic, and homoallylic alcohols, as well as secondary and tertiary alcohols, with 2 generally showing better activity and selectivity than 3. These catalytic results were compared with those previously obtained with the metal‐based catalyst Re2O7 and the benchmark acid catalyst H2SO4. The results were dependent on the substrate: By using 2, good selectivities but lower activities were generally obtained with tertiary alcohols, whereas good activities but lower selectivities were obtained with secondary alcohols. The industrially important dehydration of 2‐octanol to octenes was very efficiently catalyzed by 2. Overall, the [MoO2(acac′)2] complexes reported herein could offer a cheaper and more abundant metal‐based catalyst alternative to the previously reported rhenium‐based catalytic system for the dehydration reaction. A series of [MoO2(acac′)2] complexes have been synthesized from sodium molybdate and the desired ligand in good yields and characterized by various spectroscopic techniques and X‐ray diffraction. These complexes were found to catalyze the dehydration of various alcohols, from benzylic to aliphatic, allylic and homoallylic, to yield the corresponding olefin.