Citation: Pembere Anthony M.S., Cui Chaonan, Wu Haiming, Luo Zhixun. Small gold clusters catalyzing oxidant-free dehydrogenation of glycerol initiated by methene hydrogen atom transfer[J]. Chinese Chemical Letters, ;2019, 30(5): 1000-1004. doi: 10.1016/j.cclet.2018.12.019 shu

Small gold clusters catalyzing oxidant-free dehydrogenation of glycerol initiated by methene hydrogen atom transfer

State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, University of Chinese Academy of Sciences, Beijing 100190, China

Received Date: 9 November 2018
Revised Date: 11 December 2018
Accepted Date: 17 December 2018
Available Online: 19 May 2018

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Developing oxygen-free methodology for the conversion of alcohols to carbonyls is essentially important because it suppresses the over-oxidation of alcohols to carboxylic acids and enables the production of energetic hydrogen. Here we report a finding of feasible oxidant-free dehydrogenation of glycerol over chemically-pure Au clusters synthesized by a green chemistry method named as laser ablation in liquid (LAL). As results, glycerol is dehydrogenated to form glyceraldehyde which undergoes subsequent dehydrogenation to hydroxymethyl glyoxal. For this, reaction dynamics calculations find interesting dehydrogenation reaction pathways with a low-energy barrier of transition state initiated by hydrogen atom transfer from methene, which differs from the general reaction mechanism based on hydroxyl. Furthermore, it is interesting that the presence of additional -OH group molecules especially H₂O can effectively lower the energy barrier in the activation of the O-H and C-H bonds in glycerol. This principle is also applicable to the oxidant-free dehydrogenation of methanol and ethanol, helping to fully understand the catalytic mechanism of alcohols conversion chemistry.
- Density functional theory,
- Alcohols,
- Bond activation,
- Reaction path,
- Energy barrier
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