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Mn(III)-lodosylarene Porphyrins as an Active Oxidant in Oxidation Reactions: Synthesis, Characterization, and Reactivity Studies

Title
Mn(III)-lodosylarene Porphyrins as an Active Oxidant in Oxidation Reactions: Synthesis, Characterization, and Reactivity Studies
Authors
Guo, MianLee, Yong-MinSeo, Mi SookKwon, Yong-JuLi, Xiao-XiOhta, TakehiroKim, Won-SukSarangi, RitimuktaFukuzumi, ShunichiNam, Wonwoo
Ewha Authors
남원우이용민Shunichi Fukuzumi김원석Mian Guo
SCOPUS Author ID
남원우scopus; Shunichi Fukuzumiscopusscopus; 김원석scopus; Mian Guoscopus
Issue Date
2018
Journal Title
INORGANIC CHEMISTRY
ISSN
0020-1669JCR Link

1520-510XJCR Link
Citation
INORGANIC CHEMISTRY vol. 57, no. 16, pp. 10232 - 10240
Publisher
AMER CHEMICAL SOC
Indexed
SCIE; SCOPUS WOS scopus
Document Type
Article
Abstract
Mn(III)-iodosylarene porphyrin adducts, [Mn(III)(ArIO)(Porp)r, were synthesized by reacting electron-deficient Mn(III) porphyrin complexes with iodosylarene (ArIO) at-60 degrees C and characterized using various spectroscopic methods. The [Mn(III)(ArIO)(Porp)](+) species were then investigated in the epoxidation of olefins under stoichiometric conditions. In the epoxidation of olefins by the Mn(III)-iodosylarene porphyrin species, epoxide was formed as the sole product with high chemoselectivities and stereoselectivities. For example, cyclohexene oxide was formed exclusively with trace amounts of allylic oxidation products; cis- and trans-stilbenes were oxidized to the corresponding cis- and trans-stilbene oxides, respectively. In the catalytic epoxidation of cyclohexene by an electron-deficient Mn(M) porphyrin complex and sPhIO at low temperature (e.g.,-60 degrees C), the Mn(III)-iodosylarene porphyrin species was evidenced as the active oxidant that effects the olefin epoxidation to give epoxide as the product. However, at high temperature (e.g., 0 degrees C) or in the case of using an electron-rich manganese(III) porphyrin catalyst, allylic oxidation products, along with cyclohexene oxide, were yielded, indicating that the active oxidant(s) was not the Mn(III)-iodosylarene adduct but probably high-valent Mn-oxo species in the catalytic reactions. We also report the conversion of the Mn(III)-iodosylarene porphyrins to high-valent Mn-oxo porphyrins under various conditions, such as at high temperature, with electron-rich porphyrin ligand, and in the presence of base (01-1-). The present study reports the first example of spectroscopically well-characterized Mn(III)-iodosylarene porphyrin species being an active oxidant in the stoichiometric and catalytic oxidation reactions. Other aspects, such as one oxidant versus multiple oxidants debate, also were discussed.
DOI
10.1021/acs.inorgchem.8b01426
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자연과학대학 > 화학·나노과학전공 > Journal papers
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