TY - JOUR
T1 - Identifying Intermediates in Electrocatalytic Water Oxidation with a Manganese Corrole Complex
AU - Li, Xialiang
AU - Zhang, Xue Peng
AU - Guo, Mian
AU - Lv, Bin
AU - Guo, Kai
AU - Jin, Xiaotong
AU - Zhang, Wei
AU - Lee, Yong Min
AU - Fukuzumi, Shunichi
AU - Nam, Wonwoo
AU - Cao, Rui
N1 - Publisher Copyright:
© 2021 American Chemical Society
PY - 2021/9/15
Y1 - 2021/9/15
N2 - Water nucleophilic attack (WNA) on high-valent terminal Mn-oxo species is proposed for O-O bond formation in natural and artificial water oxidation. Herein, we report an electrocatalytic water oxidation reaction with MnIIItris(pentafluorophenyl)corrole (1) in propylene carbonate (PC). O2was generated at the MnV/IVpotential with hydroxide, but a more anodic potential was required to evolve O2with only water. With a synthetic MnV(O) complex of 1 , a second-order rate constant,k2(OH-), of 7.4 × 103M-1s-1was determined in the reaction of the MnV(O) complex of 1 with hydroxide, whereas its reaction with water occurred much more slowly with ak2(H2O) value of 4.4 × 10-3M-1s-1. This large reactivity difference of MnV(O) with hydroxide and water is consistent with different electrocatalytic behaviors of 1 with these two substrates. Significantly, during the electrolysis of 1 with water, a MnIV-peroxo species was identified with various spectroscopic methods, including UV-vis, electron paramagnetic resonance, and infrared spectroscopy. Isotope-labeling experiments confirmed that both O atoms of this peroxo species are derived from water, suggesting the involvement of the WNA mechanism in water oxidation by a Mn complex.
AB - Water nucleophilic attack (WNA) on high-valent terminal Mn-oxo species is proposed for O-O bond formation in natural and artificial water oxidation. Herein, we report an electrocatalytic water oxidation reaction with MnIIItris(pentafluorophenyl)corrole (1) in propylene carbonate (PC). O2was generated at the MnV/IVpotential with hydroxide, but a more anodic potential was required to evolve O2with only water. With a synthetic MnV(O) complex of 1 , a second-order rate constant,k2(OH-), of 7.4 × 103M-1s-1was determined in the reaction of the MnV(O) complex of 1 with hydroxide, whereas its reaction with water occurred much more slowly with ak2(H2O) value of 4.4 × 10-3M-1s-1. This large reactivity difference of MnV(O) with hydroxide and water is consistent with different electrocatalytic behaviors of 1 with these two substrates. Significantly, during the electrolysis of 1 with water, a MnIV-peroxo species was identified with various spectroscopic methods, including UV-vis, electron paramagnetic resonance, and infrared spectroscopy. Isotope-labeling experiments confirmed that both O atoms of this peroxo species are derived from water, suggesting the involvement of the WNA mechanism in water oxidation by a Mn complex.
UR - https://www.scopus.com/pages/publications/85114871152
U2 - 10.1021/jacs.1c05204
DO - 10.1021/jacs.1c05204
M3 - Article
C2 - 34469154
AN - SCOPUS:85114871152
SN - 0002-7863
VL - 143
SP - 14613
EP - 14621
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 36
ER -