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

Yamin Htet; Zhuomin Lu; Sunia A Trauger; Andrew G Tennyson

doi:10.1039/c8sc05418e

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

Chem Sci. 2018 Dec 14;10(7):2025-2033. doi: 10.1039/c8sc05418e. eCollection 2019 Feb 21.

Authors

Yamin Htet^{1

2}, Zhuomin Lu³, Sunia A Trauger⁴, Andrew G Tennyson^{3

5

6}

Affiliations

¹ Wyss Institute for Biologically Inspired Engineering , Harvard University , Cambridge , MA 02138 , USA.
² John A. Paulson School of Engineering and Applied Sciences , Harvard University , Cambridge , MA 02138 , USA.
³ Department of Chemistry , Clemson University , Clemson , SC 29634 , USA . Email: atennys@clemson.edu.
⁴ Harvard FAS Small Molecule Mass Spectrometry Facility , Harvard University , Cambridge , MA 02138 , USA.
⁵ Department of Materials Science and Engineering , Clemson University , Clemson , SC 29634 , USA.
⁶ Center for Optical Materials Science and Engineering Technologies , Anderson , SC 29625 , USA.

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.