Photocatalytic Electron-Transfer Oxidation of Triphenylphosphine and Benzylamine with Molecular Oxygen via Formation of Radical Cations and Superoxide Ion

We have recently reported that the photoexcitation of 9mesityl-10-methylacridinium ion results in ultrafast electron transfer from the Mes moiety to the singlet excited state of the Acrþ moiety to form the electron-transfer state, which has an extremely long lifetime and a high energy.36,37

Kei Ohkubo; Takashi Nanjo; Shunichi Fukuzumi

2006

Scholarcy highlights

  • In contrast to neutral free radicals, reactions of radical ions are well controlled by charges because radical cations are expected to react selectively with radical anions as compared with reactions of radical ions with the same charge
  • This back electron transfer from AÀ to Dþ can be retarded by choosing an appropriate substance, which has large reorganization energy for electron transfer
  • We have recently reported that the photoexcitation of 9mesityl-10-methylacridinium ion results in ultrafast electron transfer from the Mes moiety to the singlet excited state of the Acrþ moiety to form the electron-transfer state, which has an extremely long lifetime and a high energy
  • Photoirradiation of Acrþ–Mes gives the electron-transfer state, which can act as an oxidant for benzylamine and a reductant for molecular oxygen, resulting in the formation of a benzylamine radical cation and superoxide anion
  • When PhCH2NH2 was replaced by Ph3P, the ESR signal of the triplet contact radical ion pair between Ph3Pþ and O2À was observed, and the value of D and E were larger

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