Zhang Zhao-Yang, Ji Deyang, Mao Wenting, Cui Yu, Wang Qing, Han Lu, Zhong Hongliang, Wei Zhongming, Zhao Yixin, Nørgaard Kasper, Li Tao
School of Chemistry and Chemical Engineering and Key Laboratory of Thin Film and Microfabrication, (Ministry of Education), Shanghai Jiao Tong University, Shanghai, 200240, China.
Center for Nanotechnology, Heisenbergstraße 11, 48149, Münster, Germany.
Angew Chem Int Ed Engl. 2018 Aug 20;57(34):10949-10953. doi: 10.1002/anie.201805998. Epub 2018 Jul 20.
The +6 oxidation state of iron generally exists in the form of ferrate(VI) with high redox potential and environmentally friendly nature. Although ferrate(VI) has been known for over a century, its chemistry is still limited to the solvent-based reactions that suffers from the insolubility/instability of this oxidant and the environmental issues caused by hazardous solvents. Herein, we explore the solvent-free reactivity of ferrate(VI) under mechanical milling, revealing that its strong oxidizing power is accessible in the "dry" solid state towards a broad variety of substrates, for example, aromatic alcohols/aldehydes and carbon nanotubes. More significantly, solvent-free mechanochemistry also reshapes the oxidizing ability of ferrate(VI) due to the underlying solvent-free effect and the promotive mechanical actions. This study opens up a new chemistry of ferrate(VI) with promising application in green oxidative transformation of both organic and inorganic substrates.
铁的+6氧化态通常以高铁酸盐(VI)的形式存在,具有高氧化还原电位和环境友好的特性。尽管高铁酸盐(VI)已被发现一个多世纪,但它的化学性质仍局限于基于溶剂的反应,这种反应存在该氧化剂的不溶性/不稳定性以及有害溶剂引起的环境问题。在此,我们探索了高铁酸盐(VI)在机械研磨下的无溶剂反应活性,发现其强大的氧化能力在“干燥”固态下可作用于多种底物,例如芳香醇/醛和碳纳米管。更重要的是,由于潜在的无溶剂效应和促进性机械作用,无溶剂机械化学也重塑了高铁酸盐(VI)的氧化能力。这项研究开辟了高铁酸盐(VI)的新化学领域,在有机和无机底物的绿色氧化转化方面具有广阔的应用前景。