TY - JOUR
T1 - Remarkable Acid Catalysis in Proton-Coupled Electron-Transfer Reactions of a Chromium(III)-Superoxo Complex
AU - Devi, Tarali
AU - Lee, Yong Min
AU - Nam, Wonwoo
AU - Fukuzumi, Shunichi
N1 - Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/7/11
Y1 - 2018/7/11
N2 - Much enhanced acid catalysis was observed in oxygen atom transfer (OAT) reactions by a mononuclear nonheme Cr(III)-superoxo complex, [(Cl)(TMC)Cr III (O 2 )] + (1), in the presence of triflic acid. In the acid-catalyzed reactions, the reactivity of 1 in OAT of thioanisole was enhanced significantly, showing more than 10 4 -fold acceleration in rate. Electron transfer (ET) from electron donors to 1 also occurred only in the presence of HOTf. The enhanced reactivity of 1 by HOTf was explained by proton-coupled electron transfer from electron donors, such as ferrocene, to 1 in light of the Marcus theory of ET. The present study reports for the first time the dramatic proton effect on the chemical properties of metal-superoxo species.
AB - Much enhanced acid catalysis was observed in oxygen atom transfer (OAT) reactions by a mononuclear nonheme Cr(III)-superoxo complex, [(Cl)(TMC)Cr III (O 2 )] + (1), in the presence of triflic acid. In the acid-catalyzed reactions, the reactivity of 1 in OAT of thioanisole was enhanced significantly, showing more than 10 4 -fold acceleration in rate. Electron transfer (ET) from electron donors to 1 also occurred only in the presence of HOTf. The enhanced reactivity of 1 by HOTf was explained by proton-coupled electron transfer from electron donors, such as ferrocene, to 1 in light of the Marcus theory of ET. The present study reports for the first time the dramatic proton effect on the chemical properties of metal-superoxo species.
UR - http://www.scopus.com/inward/record.url?scp=85049409836&partnerID=8YFLogxK
U2 - 10.1021/jacs.8b02303
DO - 10.1021/jacs.8b02303
M3 - Article
C2 - 29949715
AN - SCOPUS:85049409836
SN - 0002-7863
VL - 140
SP - 8372
EP - 8375
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 27
ER -