Dioxouranium

To anhyd CuCl2 (30 mg, 0.223 mol) dissolved in anhyd DMF (2 mL) was added dioxouranium(VI) super-phthalocyanine (0.10 g, 0.11 mol), and the mixture was heated under N2 for 3 h at 120 C with stirring. After this time, the solvent was removed in vacuo and the resulting solid was washed with H20, acetone, and Et,0, and then vacuum dried to give a violet, microcrystalline powder yield 60 mg (95%). 

IV. Solvent Exchange and Ligand Substitution on the Trivalent Lanthanides and Dioxouranium(VI)... 

Although the number of actinides is the same as that of the lanthanides, their availability and chemical characteristics have so far largely restricted the study of their ligand substitution mechanisms to dioxouranium(VI), which is the ionic form of uranium most amenable to such studies in solution. In the solid state, the oxo ligands occupy axial sites above and below the U(VI) center, and four (328), five (329, 330), and six (331, 332) oxygen donor atoms have been reported to occupy equatorial positions. From a mechanistic point of view, this variability of the occupancy of the equatorial plane suggests the possibility of both d- and a-activated ligand substitution pro-... 

EXAMPLE 13.13. Name the following according to the Stock system (a) FeCl, (6) U02S04, and (c) P4O10. (a) Iron(II) chloride, (b) dioxouranium(VI) sulfate, and (c) phosphorus(V) oxide. 

Osmium(VI) forms irons-0s02(malt)2 (98), while dioxouranium(VI) forms irons-U02(malt)2 (98) and many hydroxypyridinonate complexes, with bidentate and with tetradentate (177) ligands - trans-UO2L2 and UO2L, respectively. Several actinide elements form complexes with hexa- and octa-dentate hydrox5rpyridinonates (see Section IV.C.7 later). 

Stability Constants (Log K ) for Hydroxypyronate and Hydroxy-pyridinonate Complexes of Oxovanadium(IV), Dioxovanadium(V), and Dioxouranium(VI), with Values for Cu and Zn + for Comparison... 

UO2 uranium dioxide UO2+ uranyl(l+) uranyl(v) dioxouranium( 1+) dioxouranium(v) U02 + uranyl(2+) uranyl(vi) dioxouranium(2+) dioxouranium (vi) ... 

Dioxouranium(Vl), solvent exchange and ligand substitution, 42 64-66 Dioxygen... 

Biphenyl-Diphenyl Ether Bis(Acetato)Dioxouranium Bis(2-Aminoethyl)Amine N, N-Bis(2-Aminoethyl) Ethylenediamine Bis(P-Chlorobenzoyl) Peroxide Bis(2-Chloroethyl) Ether Bis(2-Chloroethyl) Ether Bis(Dimethylthiocarbamyl) Disulfide Bis(Dimethylthiocarbamyl) Disulfide Bis(2-Ethylhexyl) Hydrogen Phosphate Bis-(2-Ethylhexyl)Hydrogen Phosphate Bis(2-Ethylhexyl) Phthalate Bis(2-Ethylhexyl)Sodium Sulfosuccinate Bis(2-(2-Hydroxyethoxy)Etlryl) Ether... 

The formates and acetates, M(RC02)4, are prepared either by reaction of the tetrachloride with the acid or (M = U) by reduction of a dioxouranium(VI) compound in non-aqueous media. The product obtained by reaction of the tetrachloride with the carboxylic acid depends on the temperature of the reaction, lower temperatures giving only partial replacement of chloride, so that compounds of the type M(RC02),C14 are obtained (see Table 27). Other... 

Table 56 Complexes of Dioxouranium(VI) Compounds with Hydrazines...

Table 57 Complexes of Ethylenediamine and other Polydentate Nitrogen Ligands with Dioxouranium(VI) Compounds...

Table 58 Some Complexes of N-Heterocyclic Ligands with Dioxouranium(Vl) Compounds...

Dipyridylalkanes. Complexes of dioxouranium(VI) compounds with these ligands are listed in Table 60. Very little is known about them. 

U04-2H20 reacts with hydrated dioxouranium(VI) oxalate, U02(C204)-H20 in the presence of aqueous alkali oxalate to form salts of peroxooxalato complex anions, M4[(U02)2(fi-02)(C204)4l (M1 = Na, K, Rb). Salts of the peroxocarbonato complex anion, [(U02)2(q-02)(C03)4], are obtained in a similar manner.234 Other reported salts of peroxooxalato and peroxocarbonato complex anions include M2[U02(02)(C204)] (M1 = Na, K, NH4),... 

The nature of these products is unknown, but they may be mixed oxidation state UV/UVI species. Dioxouranium(VI) alkoxides, U02(0R)2, and some alcohol solvates are also known, (c) Aryloxides. The only aryloxides known are the dioxouranium(VI) compounds... 

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