Synthese und Struktur des ersten Transuran-Kronenether-Einschlußkomplexes: [NpO2([18]krone-6)][ClO4]

The occurrence of the actinyl(v) species [AnO 2 ]+ (An = U, Np, Pu, Am) in the nuclear industry and in the natural environment is a particular reason for the current studies of their physicochemical properties.[ (n = 4, 5), [8] [UO 2 (H 2 O) 5 ] n+ (n = 1, 2) [9] and bare [UO 2 ] n+ ions (n = 1, 2) [8] were predicted from theoretical calculations using a variety of methods. In this context, the isolation of a pentavalent uranyl derivative, and the comparison of its crystal structure with that of its [UO 2 ] 2+ parent compound are highly desirable.In the course of our studies on the synthesis and structure of anhydrous uranyl triflate compounds, [10] Figure 1. The geometrical parameters are classical of hexavalent uranyl complexes; the linear {UO 2 } fragment is perpendicular to the equatorial plane defined by the uranium center and the four oxygen atoms of the OPPh 3 ligands. The mean U¼O bond length of 1.76(1) and the average equatorial UÀO bond length of 2.29(1) are identical to those found in [UO 2 {OP(NMe 2 ) 3 } 4 ](I 3 ) 2 . [12] In one attempt to crystallize complex 1, small red-orange, cube-shaped crystals were deposited in a small quantity along with the yellow crystals of the [UO 2 ] 2+ compound. X-ray diffraction analysis revealed that these crystals were of a new complex, the pentavalent uranyl derivative [UO 2 -(OPPh 3 ) 4 ](OTf) (2).[11] The unexpected formation of 2 requires elucidation; all attempts to produce it by reduction of 1 with UV light or various reducing agents are inconclusive at this time, and further work is in progress for controlling the synthesis of 2. Nevertheless, complex 2 was found to be kinetically stable under an inert atmosphere, which demonstrates that such [UO 2 ] + complexes can be isolated in the crystalline form, without suffering disproportionation.Crystals of 2 are composed of discrete cation-anion pairs; a view of one of the two independent [UO 2 (OPPh 3 ) 4 ]+ ions is represented in Figure 2. The cations of 1 and 2 adopt the same perfectly square bipyramidal configuration; in 2, the uranium center is located at a center of symmetry. The U ¼ O bond lengths of 1.817(6) and 1.821(6) are slightly longer than the Np¼O bond (1.797(2) ) in the isostructural [NpO 2 (OPPh 3 ) 4 ] + ion, [2] in agreement with the variation in

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Synthese und Struktur des ersten Transuran-Kronenether-Einschlußkomplexes: [NpO2([18]krone-6)][ClO4]

Cited by 9 publications

References 18 publications

Hexaphyrin(1.0.1.0.0.0): An Expanded Porphyrin Ligand for the Actinide Cations Uranyl (UO22+) and Neptunyl (NpO2+)

Hexaphyrin(1.0.1.0.0.0): An Expanded Porphyrin Ligand for the Actinide Cations Uranyl (UO22+) and Neptunyl (NpO2+)

Hexaphyrin(1.0.1.0.0.0): An Expanded Porphyrin Ligand for the Actinide Cations Uranyl (UO22+) and Neptunyl (NpO2+)

Isolation of a Uranyl [UO₂]⁺ Species: Crystallographic Comparison of the Dioxouranium(V) and (VI) Compounds [UO₂(OPPh₃)₄](OTf)_n (n=1, 2)

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Synthese und Struktur des ersten Transuran-Kronenether-Einschlußkomplexes: [NpO2([18]krone-6)][ClO4]

Cited by 9 publications

References 18 publications

Hexaphyrin(1.0.1.0.0.0): An Expanded Porphyrin Ligand for the Actinide Cations Uranyl (UO22+) and Neptunyl (NpO2+)

Hexaphyrin(1.0.1.0.0.0): An Expanded Porphyrin Ligand for the Actinide Cations Uranyl (UO22+) and Neptunyl (NpO2+)

Hexaphyrin(1.0.1.0.0.0): An Expanded Porphyrin Ligand for the Actinide Cations Uranyl (UO22+) and Neptunyl (NpO2+)

Isolation of a Uranyl [UO2]+ Species: Crystallographic Comparison of the Dioxouranium(V) and (VI) Compounds [UO2(OPPh3)4](OTf)n (n=1, 2)

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Isolation of a Uranyl [UO₂]⁺ Species: Crystallographic Comparison of the Dioxouranium(V) and (VI) Compounds [UO₂(OPPh₃)₄](OTf)_n (n=1, 2)