4.8 Article

Long-Lived Photoexcited State of a Mn(IV)-Oxo Complex Binding Scandium Ions That is Capable of Hydroxylating Benzene

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 140, Issue 27, Pages 8405-8409

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b04904

Keywords

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Funding

  1. Ministry of Education, Culture, Sports, Science and Technology (MEXT) [16H02268, 18H04650, 17H03010, 16K13964]
  2. SENTAN project from Japan Science and Technology Agency (JST)
  3. NRF of Korea through CRI [NRF-2012R1A3A2048842]
  4. GRL [NRF-2010-00353]
  5. Basic Science Research Program [2017R1D1A1B03029982, 2017R1D1A1B03032615]

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Photoexcitation of a Mn-IV-oxo complex binding scandium ions ([(Bn-TPEN)Mn-IV(O)](2+)-(Sc-(OTf3)(2)) in a solvent mixture of trifluoroethanol and acetonitrile (v/v = 1:1) resulted in formation of the longlived photoexcited state, which can hydroxylate benzene to phenol. The photohydroxylation of benzene by [(Bn-TPEN)Mn-IV(O)](2+)-(Sc(OTf3)(2) was made possible by electron transfer from benzene to the long-lived E-2 excited state of [(Bn-TPEN)Mn-IV(O)](2+)-(Sc(OTf3)(2) to produce a benzene radical cation, which reacted with water as revealed by laser-induced transient absorption measurements.

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