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F/O interactions bridge copper(I) fluorinated alkoxide complexes and facilitate dioxygen activation.
Chemistry
; 19(20): 6374-84, 2013 May 10.
Article
em En
| MEDLINE
| ID: mdl-23512253
ABSTRACT
Seven E[Cu(OR)2] copper(I) complexes (E = K(+), {K(18C6)}(+) (18C6 = [18]crown-6), or Ph4P(+); R = C4F9, CPhMe(F)2, and CMeMe(F)2) have been prepared and their reactivity with O2 studied. The K[Cu(OR)2] species react with O2 in a copper-concentration-dependent manner such that 21 and 31 Cu/O2 adducts are observed manometrically at -78 °C. Analogous reactivity with O2 is not observed with the {K(18C6)}(+) or Ph4P(+) derivatives. Solution conductivity data demonstrate that these K[Cu(OR)2] complexes do not behave as 11 electrolytes in solution. The K(+) ions induce aggregation of multiple [Cu(OR)2](-) units through Kâ
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F/O interactions and thereby effect irreversible O2 reduction by multiple Cu centers. Bond valence analyses for the potassium cations confirm the dominance of the fluorine interactions in the coordination spheres of K(+) ions. Intramolecular hydroxylation of ligand aryl and alkyl C-H bonds is observed. Nucleophilic reactivity with CO2 is observed for the oxygenated Cu complexes and a Cu(II) carbonate has been isolated and characterized.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Compostos Organometálicos
/
Cobre
/
Hidrocarbonetos Fluorados
Idioma:
En
Revista:
Chemistry
Assunto da revista:
QUIMICA
Ano de publicação:
2013
Tipo de documento:
Article
País de afiliação:
Estados Unidos