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Updated: Feb 13, 2026

Temperature-programmed Deoxygenation of Acetic Acid on Molybdenum Carbide Catalysts
Published on: February 7, 2017
Mixed-ligand complexes of paddlewheel dinuclear molybdenum as hydrodehalogenation catalysts for polyhaloalkanes
Hayato Tsurugi1, Akio Hayakawa1, Shun Kando1
1Department of Chemistry , Graduate School of Engineering Science , Osaka University , CREST , Toyonaka , Osaka 560-8531 , Japan . Email: tsurugi@chem.es.osaka-u.ac.jp ;
Abstract:
We developed a hydrodehalogenation reaction of polyhaloalkanes catalyzed by paddlewheel dimolybdenum complexes in combination with 1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene (MBTCD) as a non-toxic H-atom source as well as a salt-free reductant. A mixed-ligated dimolybdenum complex Mo2(OAc)2[CH(NAr)2]2 (3a, Ar = 4-MeOC6H4) having two acetates and two amidinates exhibited high catalytic activity in the presence of Bu4NCl, in which [ Bu4N]2[Mo2{CH(NAr)2}2Cl4] (9a), derived by treating 3a with ClSiMe3 and Bu4NCl, was generated as a catalytically-active species in the hydrodehalogenation. All reaction processes, oxidation and reduction of the dimolybdenum complex, were clarified by control experiments, and the oxidized product, [ Bu4N][Mo2{CH(NAr)2}2Cl4] (10a), was characterized by EPR and X-ray diffraction studies. Kinetic analysis of the hydrodehalogenation reaction as well as a deuterium-labelling experiment using MBTCD-d8 suggested that the H-abstraction was the rate-determining step for the catalytic reaction.
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