New uranyl(VI) complexes: binding of mono and bidentate ligands to UO2(tridentate) species

Rajan, O. A. ; Chakravorty, A. (1981) New uranyl(VI) complexes: binding of mono and bidentate ligands to UO2(tridentate) species Inorganica Chimica Acta, 50 . pp. 79-84. ISSN 0020-1693

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Official URL: http://www.sciencedirect.com/science/article/pii/S...

Related URL: http://dx.doi.org/10.1016/S0020-1693(00)83724-X

Abstract

New species of the type UO2T·D, UO2T·D·H2O and UO2T·DD are described (T = tridentate dianionic Schiff base ligand; D = monodentate donor e.g., H2O, dmf, dmso, py etc.; DD = bidentate donor e.g., 2,2′-bipyridyl). The infrared, pmr and thermal analyses data of the complexes are reported. The ν3 frequency of the dioxouranium(VI) moiety is seen in the region 880–925 cm−1. While this frequency is not very sensitive to the nature of D, on the average ν3 with D = nitrogen donor is smaller than that with D = oxygen donor. Sufficient solubility for NMR work exists only in strongly donor solvents (py or dmso). In such solutions D is displaced by the solvent. On heating, complexes generally lose H2O, D or DD in one or more steps endothermically. The DD complexes are particularly stable and loss of DD occurs only at relatively high temperatures. It is proposed that the complexes are generally pentagonal bipyramidal. The five coordination positions on the equator are occupied by the combination of T and D, H2O or DD. In the case of UO2TD a dimeric T-bridged structure is likely. The dramatic stereochemical difference between UO2T·D and MoO2T·D is noted.

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