Wolfson Materials and Catalysis Centre, School of Chemistry, University of East Anglia, Norwich NR4 7TJ, UK.
Nat Commun. 2013;4:2167. doi: 10.1038/ncomms3167.
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.
金催化剂在化学和电化学氧化过程中被广泛研究。计算模型表明，金的各种氧化态上存在与 Au-OO-Au、Au-OOH 或 Au-OH 表面物种相连的含氧物种。然而，由于分离的金过氧和过氢化合物是未知的，因此没有结构信息。在这里，我们报告了一系列金(III)过氧化物、过氢化物和过烷基化物的合成、结构和反应。过氧化物中的 Au-O 键能比氧化物和氢氧化物中的弱；然而，Au-OH 键也比 Au-H 弱。因此，Au-OH 化合物能够进行氧转移生成金氢化物，这是水分解循环中的关键反应，也是金能够以其他金属无法的方式反应的一个例子。首次有可能通过连续的氧转移事件，从过氧化物直接建立到氢化物的连接：Au-OO-Au→Au-OOH→Au-OH→Au-H。
