A Methoxylation-Promoted CPET Reaction.
Chemistry
; 29(72): e202302291, 2023 Dec 22.
Article
en En
| MEDLINE
| ID: mdl-37728426
The manuscript discloses a methoxylation reaction to an aromatic carbonyl function that carries out a CPET reaction oxidizing a transition metal ion. Spontaneous methoxylation of a redox non-innocent fragment coordinated to a high spin cobalt(II) ion, promoted concerted proton electron transfer (CPET) reaction oxidizing cobalt(II) to cobalt(III) in air and subsequent demethoxylation induced reduction of cobalt(III) to cobalt(II) producing H2 O2 are authenticated. The cobalt(III)/cobalt(II) electron transfer (ET) potential of the designed complex in CH2 Cl2 is -0.27â
V vs Fc+ /Fc redox couple. However, in presence of MeOH the reduction potential decreases to -1.02â
V due to CPET involving MeOH proton. In CH2 Cl2 /CHCl3 spontaneous demethoxylation occurs giving back the original complex and reactive methoxyl radical that reacts with O2 producing H2 O2 . Overall one molecule of MeOH produces one molecule of H2 O2 . To analyze the involvement of the proton, the rate constants of the CPET reactions in CH2 Cl2 -MeOH (2 : 1) and CH2 Cl2 -CD3 OD (2 : 1) and the demethoxylation reaction in CHCl3 at 330â
K were determined by time drive UV-Vis spectroscopy.
Texto completo:
1
Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
Chemistry
Asunto de la revista:
QUIMICA
Año:
2023
Tipo del documento:
Article
País de afiliación:
India
Pais de publicación:
Alemania