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Dioxygen Activation and O-O Bond Formation Reactions by Manganese Corroles

Title
Dioxygen Activation and O-O Bond Formation Reactions by Manganese Corroles
Authors
Guo M.Lee Y.-M.Gupta R.Seo M.S.Ohta T.Wang H.-H.Liu H.-Y.Dhuri S.N.Sarangi R.Fukuzumi S.Nam W.
Ewha Authors
남원우Shunichi Fukuzumi
SCOPUS Author ID
남원우scopus; Shunichi Fukuzumiscopus
Issue Date
2017
Journal Title
Journal of the American Chemical Society
ISSN
0002-7863JCR Link
Citation
vol. 139, no. 44, pp. 15858 - 15867
Publisher
American Chemical Society
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
Activation of dioxygen (O2) 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 O2-activation reaction, has been the focus of current research. Herein, we report the O2-activation and O-O bond formation reactions by manganese corrole complexes. In the O2-activation reaction, Mn(V)-oxo and Mn(IV)-peroxo intermediates were formed when Mn(III) corroles were exposed to O2 in the presence of base (e.g., OH-) and hydrogen atom (H atom) donor (e.g., THF or cyclic olefins); the O2-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 O2 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 O2-activation and O-O bond formation reactions. © 2017 American Chemical Society.
DOI
10.1021/jacs.7b08678
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자연과학대학 > 화학·나노과학전공 > Journal papers
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