Functional Synthetic Model for the Lanthanide-Dependent Quinoid Alcohol Dehydrogenase Active Site

The oxidation of
methanol by dehydrogenase enzymes is an essential
part of the bacterial methane metabolism cycle. The recent discovery
of a lanthanide (Ln) cation in the active site of the XoxF dehydrogenase
represents the only example of a rare-earth element in a physiological
role. Herein, we report the first synthetic, functional model of Ln-dependent
dehydrogenase and its stoichiometric and catalytic dehydrogenation
of a benzyl alcohol. Density functional theory calculations implicate
a hydride transfer mechanism for these reactions.