Detailed characterization of dioxouranium(vi) complexes with a symmetrical tetradentate N2 O2 -benzil bis(isonicotinoyl hydrazone) ligand

Dalton Transactions : an International Journal of Inorganic Chemistry
Sipun SethiNabakrushna Behera

Abstract

The reactions of UO2(OAc)2·2H2O with benzil bis(isonicotinoyl hydrazone) ligand (H2L) in varied solvent media resulted in the formation of a series of new dioxouranium(vi) complexes 1-3 of the type UO2(L)(X), [where 1, X = DMF; 2, X = DMSO; 3, X = H2O]. The complexes were systematically characterized by elemental analysis, UV-Visible spectroscopy, TGA, mass spectrometry, cyclic voltammetry, and powder X-ray diffraction study. Among all the complexes, 1 was confirmed by single-crystal X-ray diffraction study. It was found that 1 preferred a distorted pentagonal bipyramidal geometry, in which an equatorial coordination plane was formed by the ONNO-tetradentate cavity of the deprotonated hydrazone ligand along with an additional oxygen atom of the coordinated solvent molecule. Thermal analysis suggested that complexes 1 and 3 undergo weight loss in the temperature range 180-210 °C and 100-120 °C, respectively, due to the ready release of their coordinated solvent molecules. Complexes 1-3 exhibited analogous UV-Visible absorption bands and the intense band between 300-600 nm was assigned to the M ← L and n → π* transitions. Weakly resolved reduction waves assigned to {UO2}2+/{UO2}+ couple were observed for complexes 1 and 2 {1, -1....Continue Reading

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WinGx
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