Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 139, Issue 44, Pages 15858-15867Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b08678
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Funding
- NRF of Korea through CRI [NRF-2012R1A3A2048842]
- GRL [NRF-2010-00353]
- Basic Science Research Program [2017R1D1A1B03029982, 2017R1D1A1B03032615]
- Ministry of Education, Culture, Sports, Science and Technology (MEXT) [16H02268]
- SENTAN project from the Japan Science and Technology Agency (JST)
- National Natural Science Foundation of China [21371059, 21671068]
- NIH National Institute of General Medical Sciences (NIGMS) through a Biomedical Technology Research Resource P41 grant [P41GM103393]
- DOE Office of Biological and Environmental Research
- National Research Foundation of Korea [2012R1A3A2048842, 2017R1D1A1B03032615, 2010-00353] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
- Grants-in-Aid for Scientific Research [16K05850, 16H02268] Funding Source: KAKEN
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Activation of dioxygen (O-2) in enzymatic and biomimetic reactions has been intensively investigated over the past several decades. More recently, O-O bond formation, which is the reverse of the O-2-activation reaction, has been the focus of current research. Herein, we report the O-2-activation and O-O bond formation reactions by manganese corrole complexes. In the O-2-activation reaction, Mn(V)-oxo and Mn(IV)-peroxo intermediates were formed when Mn(III) corroles were exposed to O-2 in the presence of base (e.g., OH-) and hydrogen atom (H atom) donor (e.g., THE or cyclic olefins); the O-2-activation reaction did not occur in the absence of base and H atom donor. Moreover, formation of the Mn(V)-oxo and Mn(IV)-peroxo species was dependent on the amounts of base present in the reaction solution. The role of the base was proposed to lower the oxidation potential of the Mn(III) corroles, thereby facilitating the binding of O-2 and forming a Mn(IV)-superoxo species. The putative Mn(IV)-superoxo species was then converted to the corresponding Mn(IV)-hydroperoxo species by abstracting a H atom from H atom donor, followed by the O-O bond cleavage of the putative Mn(IV)-hydroperoxo species to form a Mn(V)-oxo species. We have also shown that addition of hydroxide ion to the Mn(V)-oxo species afforded the Mn(IV)-peroxo species via O-O bond formation and the resulting Mn(IV)-peroxo species reverted to the Mn(V)-oxo species upon addition of proton, indicating that the O-O bond formation and cleavage reactions between the Mn(V)-oxo and Mn(IV)-peroxo complexes are reversible. The present study reports the first example of using the same manganese complex in both O-2-activation and O-O bond formation reactions.
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