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Carboxylate complexes of the early actinides
Başlık:
Carboxylate complexes of the early actinides
Yazar:
Silverwood, Paul Richard, author.
ISBN:
9780438043497
Yazar Ek Girişi:
Fiziksel Tanımlama:
1 electronic resource (284 pages)
Genel Not:
Source: Dissertation Abstracts International, Volume: 76-08C.
Özet:
This thesis contains a selective and critical review of the coordination chemistry of the Th4+ and UO22+ cations with a family of ligands, which contain carboxylate and other potential donor groups. The crystal structures of [UO2(Hheb) 2 (H2O)].2H2O, [UO2 (Hpmida) 2].5H2O, [UO2 (NO3)].2[UO2 (mpa) 2 (H2O)].2H2O,[UO2 (dpa)(H2O)]n and [Th(dpa)2(H2O)4] are presented, along with the details of similar representative structures. These are used as calibration tools for the other solid state analytical and spectroscopic techniques, which are then used to characterise a range of other complexes and compounds for which XRD data are not available. Microanalysis predicts the ratio of actinide : organic proligand / ligand : water : counter-ion. Thermal analysis attempts to discriminate different water environments from their temperature of expulsion (lattice water at approx, 25-140 °C or coordinated water 140-180 °C) and identifies the presence of counter-ions and proligand molecules within the crystal lattice (endothermic changes at 200-300 °C). Infrared spectroscopy provides evidence for the coordination of the carboxylate groups and suggests their number and mode of coordination. It also suggests the presence of An-N bonds (410-420 cm-1) and predicts the equatorial coordination number of the uranyl groups: {4} 937-960 cm-1; {5} 923-937 cm-1; and {6} 895-923 cm-1 Solid state13 C NMR is reasonably diagnostic of the different modes of carboxylate coordination (monodentate, bridging bidentate or 1,3-bidentate to the same metal centre). Five-membered chelate rings are common structural features, but not exclusive; rings containing 4 to 8 atoms are sjmthesised. Finally, selective precipitation of either UO22+ (with Hmpa or H2cma) or Th4+ (with H2icm or H2dna) from aqueous solution is demonstrated.
Notlar:
School code: 1543
Tüzel Kişi Ek Girişi:
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Yer Numarası | Demirbaş Numarası | Shelf Location | Lokasyon / Statüsü / İade Tarihi |
---|---|---|---|
XX(684286.1) | 684286-1001 | Proquest E-Tez Koleksiyonu | Arıyor... |
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