Please use this identifier to cite or link to this item: http://hdl.handle.net/10773/37535
Title: Synthesis, characterization, spectral and catalytic activity of tetradentate (NNNO) azo-imine Schiff base copper(II) complexes
Author: Pratihar, Jahar Lal
Mandal, Paritosh
Brandão, Paula
Mal, Dasarath
Félix, Vítor
Keywords: Copper(II)
C=N bond cleavage
Crystal structures
Redox
Emission
Oxidation reactions
Issue Date: 1-Jul-2018
Publisher: Elsevier
Abstract: The hexadentate ligand, 2,2′-bis(salicylideneamino)azobenzene, 1 has been synthesized from 2,2′-diaminoazobenzene and salicylaldehyde in refluxing diethyl ether. Reaction of ligand 1 with Cu(II) acetate and Cu(II) perchlorate separately in methanol afforded tetradentate (N,N,N,O) Cu(II) complexes, Cu(L) & [Cu(HL)]ClO4 respectively [where H2L represent the one imine moiety cleavage product of ligand 1 (H represents the dissociable amino and phenolic protons)]. These were characterized by microanalytical data and spectroscopic studies. In addition, the crystal structures of the ligand 1 and complexes Cu(L) & [Cu(HL)]ClO4 were determined by X-ray diffraction analysis. The diffraction analysis revealed that the ligand (H2L) binds Cu(II) centers in (N,N,N,O) tetra dentate fashion in distorted square planer geometry. In complex [Cu(HL)]ClO4 the apical position of copper center is weakly coordinated with one perchlorate ion. The dimeric structure of the molecule [Cu(HL)]ClO4 is stabilized through NH2···O hydrogen bonds. The fluorescence and redox property of ligand 1 and complexes Cu(L) & [Cu(HL)]ClO4 were studied. Preliminary DFT calculations were carried out using crystallographic coordinates to understand the electronic spectra and redox properties of the ligand and complexes. The complex Cu(L) shows very good catalytic activities towards oxidation of benzyl alcohol to benzaldeyhde (under solvent-free condition) and organic thioethers to sulfoxide and sulfones using H2O2 as the oxidant.
Peer review: yes
URI: http://hdl.handle.net/10773/37535
DOI: 10.1016/j.ica.2018.04.042
ISSN: 0020-1693
Appears in Collections:CICECO - Artigos
DQ - Artigos

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