TY - JOUR
T1 - Unprecedented Reactivities of Highly Reactive Manganese(III)-Iodosylarene Porphyrins in Oxidation Reactions
AU - Zhang, Lina
AU - Lee, Yong Min
AU - Guo, Mian
AU - Fukuzumi, Shunichi
AU - Nam, Wonwoo
N1 - Funding Information:
This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842).
Publisher Copyright:
© 2020 American Chemical Society.
PY - 2020/11/25
Y1 - 2020/11/25
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85096573079&partnerID=8YFLogxK
U2 - 10.1021/jacs.0c10159
DO - 10.1021/jacs.0c10159
M3 - Article
C2 - 33186008
AN - SCOPUS:85096573079
SN - 0002-7863
VL - 142
SP - 19879
EP - 19884
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 47
ER -