期刊
COORDINATION CHEMISTRY REVIEWS
卷 334, 期 -, 页码 25-42出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ccr.2016.07.006
关键词
Metalloenzymes; Biomimetics; Dioxygen activation; Metal-oxygen intermediate; Nonheme models
资金
- NRF of Korea through the CRI [NRF-2012R1A3A2048842]
- NRF of Korea through the GRL [NRF-2010-00353]
- Cluster of Excellence Unifying Concepts in Catalysis, Berlin [EXC 314/2]
- Heisenberg-Programm of the Deutsche Forschungsgemeinschaft
- National Research Foundation of Korea [2010-00353, 2012R1A3A2048842] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
The activation of dioxygen (O-2) by metalloenzymes proceeds by binding O-2 at their active sites and then generating highly reactive, thermally unstable metal-oxygen intermediates, such as metal-superoxo, -(hydro)peroxo and-oxo species, via electron and proton transfer reactions. The synthesis, characterization and reactivity studies of the chemical model compounds of the key metal-oxygen intermediates can provide vital insights into the chemistry of such enzymatic reactions, and our understanding of the biologically important metal-oxygen intermediates has improved greatly by the success of synthesizing their analogues recently. In this article, we provide a focused review on the recent advances in the dioxygen activation processes at biomimetic iron, copper and chromium centers, paying particular emphasis to the factors that control the O-2-activation reactions, such as the effects of ligands, redox potentials and spin-states of biomimetic compounds. Among the most significant findings of these studies are the use of O-2 as an oxygen source in the generation of iron-oxygen intermediates and the autocatalytic radical chain reactions involved in the iron-mediated O-2-activation processes. Similarly, new approaches to achieve less overpotential have been identified, which is more desirable for the catalytic four-electron reduction of O-2 using copper complexes. In addition, the versatility of metal-superoxo species as reactive intermediates in various oxidation reactions has been elegantly demonstrated in the recent synthesis of a mononuclear nonheme chromium(III)-superoxo complex. This review will provide clues that lesson us how synthetic and mechanistic developments in biomimetic research can advance our understanding of O-2-activation processes in enzymatic reactions. (C) 2016 Elsevier B.V. All rights reserved.
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