Hydrogen peroxide as a hydride donor and reductant under biologically relevant conditions

Abstract

Some ruthenium-hydride complexes react with O2 to yield H2O2, therefore the principle of microscopic reversibility dictates that the reverse reaction is also possible, that H2O2 could transfer an H− to a Ru complex. Mechanistic evidence is presented, using the Ru-catalyzed ABTS− reduction reaction as a probe, which suggests that a Ru-H intermediate is formed via deinsertion of O2 from H2O2 following coordination to Ru. This demonstration that H2O2 can function as an H− donor and reductant under biologically-relevant conditions provides the proof-of-concept that H2O2 may function as a reductant in living systems, ranging from metalloenzyme-catalyzed reactions to cellular redox homeostasis, and that H2O2 may be viable as an environmentally-friendly reductant and H− source in green catalysis.