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A structural study on uranyl (VI) nitrate complexes with cyclic amides: N-n-butyl-2-pyrrolidone, N-cyclohexylmethyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidone |
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| Authors: | Nobuyoshi Koshino Masayuki Harada Yasuji Morita Yasuhisa Ikeda |
| Institution: | a Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1-N1-34 O-okayama, Meguro-ku, Tokyo 152-8550, Japan b Institute of Research and Innovation, 1201 Takada, Kashiwa, Chiba 277-0861, Japan c Japan Atomic Energy Research Institute, Tokai-mura, Naka-gun, Ibaraki 319-1195, Japan d Mitsubishi Materials Corporation, 1-297 Kitabukuro-cho, Oomiya-ku, Saitama 330-8508, Japan |
| Abstract: | Structural analyses of UO2(NO3)2L2 L = N-n-butyl-2-pyrrolidone (NBP), N-cyclohexylmethyl-2-pyrrolidone (NCMeP), and 1,3-dimethyl-2-imidazolidone (DMI)] have been carried out using X-ray diffraction method. These uranyl complexes were found to have a hexagonal bipyramidal structure. The bond distances (Å) of U O and U-O(ligand), and bond angles (°) of U-O-C(carbonyl) are determined as follows: 1.774(2), 2.374(2), and 137.6(2) for UO2(NO3)2(NBP)2; 1.770(1), 2.383(2), and 135.3(1) for UO2(NO3)2(NCMeP)2; 1.771(2), 2.361(2), and 143.3(2) for UO2(NO3)2(DMI)2. In uranyl nitrate complexes with cyclic amides such as 2-pyrrolidone, urea, and caprolactam derivatives, a linear correlation was found to hold between U-O(ligand) bond distances and U-O-C(carbonyl) bond angles. Vibrational frequencies of UO2(NO3)2L2 have also been measured by IR and Raman spectrophotometers. Using relationships between vibrational frequencies of OUO bonds and donor numbers (DNs) of ligands, it was found that donicities of N-substituted-2-pyrrolidones (Me, Et, Bu, cyclohexyl, and cyclohexylmethyl) are in the range of 26-29, and the DN of 1,3-dimethyl-2-imidazolidone was estimated as 27.8. |
| Keywords: | Uranyl nitrate complexes Pyrrolidone derivatives Imidazolidone derivatives Crystal structures Donor number |
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