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RESEARCH PRODUCT

Synthesis and chemical characterization of CuII, NiII and ZnII complexes of 3,5-bis(2′-pyridyl)-1,2,4-oxadiazole and 3-(2′-pyridyl)5-(phenyl)-1,2,4-oxadiazole ligands

Giampaolo BaroneAnnalisa GuarcelloAntonio Palumbo PiccionelloAndrea PaceAlessio TerenziGianluca Giorgi

subject

Ligand field theoryStereochemistryOxadiazoleCrystal structureCarbon-13 NMRInorganic ChemistryNMR spectra databasechemistry.chemical_compoundCrystallographychemistryPyridineMaterials ChemistryMoleculePhysical and Theoretical ChemistryCoordination geometry

description

Abstract The synthesis and structural characterization of Ni II , Cu II and Zn II complexes of two chelating 1,2,4-oxadiazole ligands, namely 3,5-bis(2′-pyridyl)-1,2,4-oxadiazole (bipyOXA) and 3-(2′-pyridyl)5-(phenyl)-1,2,4-oxadiazole (pyOXA), is here reported. The formed hexacoordinated metal complexes are [M(bipyOXA) 2 (H 2 O) 2 ](ClO 4 ) 2 and [M(pyOXA) 2 (ClO 4 ) 2 ], respectively (M = Ni, Cu, Zn). X-ray crystallography, 1 H and 13 C NMR spectroscopy and C, N, H elemental analysis data concord in attributing them an octahedral coordination geometry. The two coordinated pyOXA ligands assume a trans coplanar disposition, while the two bipyOXA ligands are not. The latter result is a possible consequence of the formation of H-bonds between the coordinated water molecules and the nitrogen atom of the pyridine in position 5 of the oxadiazole ring. The expected splitting of the d metal orbitals in an octahedral ligand field explains the observed paramagnetism of the d 8 and d 9 electron configuration of the nickel(II) and copper(II) complexes, respectively, as determined by the broadening of their NMR spectra.

https://doi.org/10.1016/j.ica.2011.03.057