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

Journal Article · · Inorganic Chemistry
 [1];  [1];  [1];  [1];  [1];  [2];  [1];  [3];  [1];  [4]
  1. Ewha Womans Univ., Seoul (Korea)
  2. Univ. of Hyogo, Hyogo (Japan)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Ewha Womans Univ., Seoul (Korea); Shaanxi Normal Univ., Xi'an (People's Republic of China)
+ Show Author Affiliations

Mn(III)-iodosylarene porphyrin adducts, [Mn(III)(ArIO)(Porp)]+, were synthesized by reacting electron-deficient Mn(III) porphyrin complexes with iodosylarene (ArIO) at –60 °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(III) porphyrin complex and sPhIO at low temperature (e.g., –60 °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 °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 (OH–). 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. In conclusion other aspects, such as one oxidant versus multiple oxidants debate, also were discussed.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1476114
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 16 Vol. 57; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (4)

Structure and Unprecedented Reactivity of a Mononuclear Nonheme Cobalt(III) Iodosylbenzene Complex journal May 2020
Structure and Unprecedented Reactivity of a Mononuclear Nonheme Cobalt(III) Iodosylbenzene Complex journal May 2020
Enhancing catalytic alkane hydroxylation by tuning the outer coordination sphere in a heme-containing metal–organic framework journal January 2020
Synthesis of nanorod MOF catalyst containing Cu 2+ and its selective oxidation of styrene journal November 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY