Electrochemically mediated DODH in early transition metal-dioxo complexes

by Canote, Cody; Kilyanek, Stefan M.

Biomass up-conversion to commodity chems. may be an essential tool in reducing chem. industry's reliance on petroleum feedstocks. Two known deoxydehydration (DODH) catalysts, Cis-dioxo[2,6-pyridinedicarboxylato](hexamethylphos-phoramide)molybdenum, 1, [Tetrabutylammonium]-[cis-dioxo[2,6-pyridinedicarboxylato]vanadium], 2, have previously shown promise as homogeneous catalysts at high temperatures using sacrificial reductants. This work studies the electrochem. behavior of these complexes and their subsequent reactivity towards vicinal diols. Both have demonstrated reduction via proton-coupled electron transfer and 1 has successfully reduced 1-phenyl-1,2-ethanediol to styrene without the need for stoichiometric reductant. Further work will study the electrochem. mediated DODH in 2 and other metal-oxo complexes synthesized by our group.