Four-electron oxygen reduction by tetrathiafulvalene

Astrid J Olaya; Peiyu Ge; Jérôme F Gonthier; Peter Pechy; Clémence Corminboeuf; Hubert H Girault

doi:10.1021/ja203251u

Four-electron oxygen reduction by tetrathiafulvalene

J Am Chem Soc. 2011 Aug 10;133(31):12115-23. doi: 10.1021/ja203251u. Epub 2011 Jul 19.

Authors

Astrid J Olaya¹, Peiyu Ge, Jérôme F Gonthier, Peter Pechy, Clémence Corminboeuf, Hubert H Girault

Affiliation

¹ Laboratoire d'Electrochimie Physique et Analytique, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland.

PMID: 21714519
DOI: 10.1021/ja203251u

Abstract

The four-electron reduction of oxygen by tetrathiafulvalene (TTF) in acidified 1,2-dichloroethane and at the acidified water/1,2-dichloroethane interface has been observed. Spectroscopy and ion transfer voltammetry results suggest that the reaction proceeds by the fast protonation of TTF followed by the 4-electron reduction of oxygen to form water. Electronic structure computations give evidence of the formation of a helical tetramer assembly ([TTF(4)H(2)](2+)) of two protonated TTF and two neutral TTF molecules. The protonated tetramer is potentially able to deliver the four electrons needed for the oxygen reduction. The production of water was corroborated by (1)H NMR analysis.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Electrons*
Heterocyclic Compounds / chemistry*
Magnetic Resonance Spectroscopy
Models, Molecular
Molecular Structure
Oxidation-Reduction
Oxygen / chemistry*
Quantum Theory
Stereoisomerism

Substances

Heterocyclic Compounds
tetrathiafulvalene
Oxygen