Gold peroxide complexes and the conversion of hydroperoxides into gold hydrides by successive oxygen-transfer reactions

Dragoş-Adrian Roşca, Joseph A. Wright, David L. Hughes and Manfred Bochmann ()
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Dragoş-Adrian Roşca: Wolfson Materials and Catalysis Centre, School of Chemistry, University of East Anglia
Joseph A. Wright: Wolfson Materials and Catalysis Centre, School of Chemistry, University of East Anglia
David L. Hughes: Wolfson Materials and Catalysis Centre, School of Chemistry, University of East Anglia
Manfred Bochmann: Wolfson Materials and Catalysis Centre, School of Chemistry, University of East Anglia

Nature Communications, 2013, vol. 4, issue 1, 1-7

Abstract: Abstract Gold catalysts are widely studied in chemical and electrochemical oxidation processes. Computational modelling has suggested the participation of Au–OO–Au, Au–OOH or Au–OH surface species, attached to gold in various oxidation states. However, no structural information was available as isolable gold peroxo and hydroperoxo compounds were unknown. Here we report the syntheses, structures and reactions of a series of gold(III) peroxides, hydroperoxides and alkylperoxides. The Au–O bond energy in peroxides is weaker than in oxides and hydroxides; however, the Au–OH bond is also weaker than Au–H. Consequently Au–OH compounds are capable of oxygen-transfer generating gold hydrides, a key reaction in a water splitting cycle and an example that gold can react in a way that other metals cannot. For the first time it has become possible to establish a direct connection from peroxides to hydrides: Au–OO–Au→Au–OOH→Au–OH→Au–H, via successive oxygen-transfer events.

Date: 2013
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DOI: 10.1038/ncomms3167

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