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3,5-Lutidine coordinated zinc(II) aryl carboxylate complexes: Precursors for zinc(II) oxide
Authors:Umesh Kumar  Rajamani Nagarajan
Institution:a Department of Chemistry, University of Delhi, Delhi 110007, India
b Department of Chemistry, Indian Institute of Technology Delhi, Delhi 110016, India
Abstract:The reaction of Zn(κ2O,O′-OAc)2·2H2O with two equiv of 3,5-lutidine in methanol at room temperature for 12 h afforded Zn(OAc)2(3,5-lutidine)2]· H2O (1) in 91% yield. The acetate exchange reaction of 1 with two equiv of aryl carboxylic acids in methanol at room temperature for 12 h afforded Zn(μ2-κ1O:κ1O′-O2CAr)2(3,5-lutidine)]2 Ar = C6H5 (2) and C6H4Me-3 (3)], Zn(OC(O)C6H4Me-2)2(3,5-lutidine)2] (4) and Zn(κ2O,O′−O2CC6H4Me-4)2(3,5-lutidine)2] (5) in ?90% yield. Complexes 1-5 were characterized by microanalytical, IR, solution (1H and 13C) and solid-state cross-polarization magic angle spinning 13C NMR and X-ray diffraction data. The zinc atom in 1 is surrounded by nitrogen atom of two 3,5-lutidine and oxygen atom of two monodentate acetate moiety and thus attains a tetrahedral geometry. One of the acetate moieties is hydrogen bonded with a water molecule in the crystal lattice. Complexes 2 and 3 possess a dinuclear paddlewheel framework with a square pyramidal geometry around the zinc atom whereas 4 and 5 are mononuclear species with the zinc atom in tetrahedral and an octahedral geometry, respectively. Thermogravimetric analyses of 2-5 suggested ZnO as the decomposed product followed by the confirmation from the powder X-ray diffraction patterns. Enormous gas evolution resulting in porous ZnO during thermal decomposition was evidenced from scanning electron microscopic images.
Keywords:Zinc(II) aryl carboxylates  3  5-Lutidine  Acetate exchange reaction  Thermal decomposition studies  ZnO
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