Air oxygenation chemistry of 4-TBC catalyzed by chloro bridged dinuclear copper(ii) complexes of pyrazole based tridentate ligands: synthesis, structure, magnetic and computational studies.
ABABEI, Rodica
Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
Centre de recherches Paul Pascal [CRPP]
< Leer menos
Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
Centre de recherches Paul Pascal [CRPP]
Idioma
en
Article de revue
Este ítem está publicado en
Dalton Transactions. 2013, vol. 42, n° 5, p. pp. 1879-1892
Royal Society of Chemistry
Resumen en inglés
Four dinuclear bis(μ-Cl) bridged copper(ii) complexes, [Cu(2)(μ-Cl)(2)(L(X))(2)](ClO(4))(2) (L(X) = N,N-bis[(3,5-dimethylpyrazole-1-yl)-methyl]benzylamine with X = H(1), OMe(2), Me(3) and Cl(4)), have been synthesized and ...Leer más >
Four dinuclear bis(μ-Cl) bridged copper(ii) complexes, [Cu(2)(μ-Cl)(2)(L(X))(2)](ClO(4))(2) (L(X) = N,N-bis[(3,5-dimethylpyrazole-1-yl)-methyl]benzylamine with X = H(1), OMe(2), Me(3) and Cl(4)), have been synthesized and characterized by the single crystal X-ray diffraction method. In these complexes, each copper(ii) center is penta-coordinated with square-pyramidal geometry. In addition to the tridentate L(X) ligand, a chloride ion occupies the last position of the square plane. This chloride ion is also bonded to the neighboring Cu(ii) site in its axial position forming an SP-I dinuclear Cu(ii) unit that exhibits small intramolecular ferromagnetic interactions and supported by DFT calculations. The complexes 1-3 exhibit methylmonooxygenase (pMMO) behaviour and oxidise 4-tert-butylcatechol (4-TBCH(2)) with molecular oxygen in MeOH or MeCN to 4-tert-butyl-benzoquinone (4-TBQ), 5-methoxy-4-tert-butyl-benzoquinone (5-MeO-4-TBQ) as the major products along with 6,6'-Bu(t)-biphenyl-3,4,3',4'-tetraol and others as minor products. These are further confirmed by ESI- and FAB-mass analyses. A tentative catalytic cycle has been framed based on the mass spectral analysis of the products and DFT calculations on individual intermediates that are energetically feasible.< Leer menos
Palabras clave en inglés
Dinuclear bis(μ-Cl) bridged
Copper(ii) complexes
Chemical synthesis
Single crystal X-ray diffraction
DFT calculations
ESI- and FAB-mass analyses
Orígen
Importado de HalCentros de investigación