Bioinduced Room-Temperature Methanol Reforming

M.Sc. Leo E. Heim¹, Dipl.-Chem. Daniel Thiel¹, Christian Gedig¹, Priv.-Doz. Dr. Jan Deska^1,2,* andPriv.-Doz. Dr. Martin H. G. Prechtl^1,*
1.Department Chemie, Universität zu Köln, Greinstrasse 4-6, 50939 Cologne (Germany)
2.Current address: Department of Chemistry, Aalto University, Kemistintie 1, 00076 Espoo (Finland)

Article first published online: 14 JUL 2015

DOI: 10.1002/anie.201503737

Abstract

Imitating nature′s approach in nucleophile-activated formaldehyde dehydrogenation, air-stable ruthenium complexes proved to be exquisite catalysts for the dehydrogenation of formaldehyde hydrate as well as for the transfer hydrogenation to unsaturated organic substrates at loadings as low as 0.5 mol %. Concatenation of the chemical hydrogen-fixation route with an oxidase-mediated activation of methanol gives an artificial methylotrophic in vitro metabolism providing methanol-derived reduction equivalents for synthetic hydrogenation purposes. Moreover, for the first time methanol reforming at room temperature was achieved on the basis of this bioinduced dehydrogenation path delivering hydrogen gas from aqueous methanol.

Imitating nature′s approach for nucleophile-activated formaldehyde dehydrogenation: Air-stable ruthenium complexes are catalysts for the dehydrogenation of formaldehyde hydrate as well as for the transfer hydrogenation to unsaturated organic substrates. In combination with an oxidase-mediated activation of methanol, an artificial methylotrophic in vitro metabolism provides hydrogen gas in a room-temperature methanol-reforming pathway.

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