Deoxydehydration (DODH) of poylols to alkenes and dienes can be achieved by metal-oxo catalysts. DODH is a possible route for the conversion of biomass-derived materials to carbon-based industrial feedstocks such as olefins and dienes. Catalyst activity is closely tied to the speciation of the system, the electronic properties of the substrate and the identity of the reductant. Dioxo(pyridine-2,6-dicarboxylato)(hexamethylphosphoramide) molybdenum (VI) was found to be a competent DODH catalyst. The kinetics and mechanism of the DODH of 2-phenyl-1,2-ethandiol was studied by NMR and in situ IR spectroscopy. Several mechanisms were found to be feasible pathways to the observed products. The ratio of alkenes to aldehyde products was found to depend on the electronic properties of the alkenes and the mechanism of reduction. A variety of reductants were studied, including PPh3 Na2SO3, Zn, C and CO. The speciation of the DODH systems were study by Diffusion-Ordered NMR spectroscopy (DOSY NMR). The electrochemical behavior of the catalyst systems were also surveyed. Additionally, related tungsten complexes were examined.

Mechanistic studies of the deoxydehydration of polyols by group VI transition metal catalysts

253rd National Meeting (2017)

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