Halide-promoted dioxygenolysis of a carbon-carbon bond by a copper(II) diketonate complex.
J Am Chem Soc
; 136(22): 7821-4, 2014 Jun 04.
Article
em En
| MEDLINE
| ID: mdl-24826946
ABSTRACT
A mononuclear Cu(II) chlorodiketonate complex was prepared, characterized, and found to undergo oxidative aliphatic carbon-carbon bond cleavage within the diketonate unit upon exposure to O2 at ambient temperature. Mechanistic studies provide evidence for a dioxygenase-type C-C bond cleavage reaction pathway involving trione and hypochlorite intermediates. Significantly, the presence of a catalytic amount of chloride ion accelerates the oxygen activation step via the formation of a Cu-Cl species, which facilitates monodentate diketonate formation and lowers the barrier for O2 activation. The observed reactivity and chloride catalysis is relevant to Cu(II) halide-catalyzed reactions in which diketonates are oxidatively cleaved using O2 as the terminal oxidant. The results of this study suggest that anion coordination can play a significant role in influencing copper-mediated oxygen activation in such systems.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Carbono
/
Cobre
/
Halogênios
/
Cetonas
Idioma:
En
Revista:
J Am Chem Soc
Ano de publicação:
2014
Tipo de documento:
Article
País de afiliação:
Estados Unidos