Abstract
We report that Mn(III)-iodosylarene porphyrins, [MnIII(Porp)(sArIO)]+, are capable of activating the C-H bonds of hydrocarbons, including unactivated alkanes such as cyclohexane, with unprecedented reactivities, such as a low kinetic isotope effect, a saturation behavior of reaction rates, and no electronic effect of porphyrin ligands on the reactivities of [MnIII(Porp)(sArIO)]+. In oxygen atom transfer (OAT) reactions, the sulfoxidation of para-X-substituted thioanisoles by [MnIII(Porp)(sArIO)]+ affords a very unusual behavior in the Hammett plot with the saturation behavior of reaction rates and no electronic effect of porphyrin ligands on reactivities. The reactivities and mechanisms of [MnIII(Porp)(sArIO)]+ are then compared with those of the corresponding MnIV(Porp)(O) complex. The present study reports the first example of highly reactive Mn(III)-iodosylarene porphyrins with unprecedented reactivities in C-H bond activation and OAT reactions.
Original language | English |
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Pages (from-to) | 19879-19884 |
Number of pages | 6 |
Journal | Journal of the American Chemical Society |
Volume | 142 |
Issue number | 47 |
DOIs | |
State | Published - 25 Nov 2020 |
Bibliographical note
Funding Information:This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842).
Publisher Copyright:
© 2020 American Chemical Society.