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Radiochimica Acta

International Journal for chemical aspects of nuclear science and technology

Ed. by Qaim, Syed M.

12 Issues per year


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First 5f-element complexes with the tetradentate BTBP ligand. Synthesis and crystal structure of uranyl(VI) compounds with CyMe4BTBP

Jean-Claude Berthet / P. Thuéry / M. R. S. Foreman / Michel Ephritikhine

Citation Information: Radiochimica Acta. Volume 96, Issue 4-5/2008, Pages 189–197, ISSN (Print) 0033-8230, DOI: 10.1524/ract.2008.1478, September 2009

Publication History

Received:
2007-04-26
Accepted:
2007-06-13
Published Online:
2009-09-25

Treatment of [UO2(OTf)2] or [UO2I2(thf)3] with 1 equiv. of CyMe4BTBP in anhydrous acetonitrile led to the formation of [UO2(CyMe4BTBP)(OTf)2] (1) and [UO2(CyMe4BTBP)I2] (2) which crystallized as the cationic forms [UO2(CyMe4BTBP)(py)][OTf]2 (3) and [UO2I(CyMe4BTBP)][I] (4) in pyridine and acetonitrile, respectively. These compounds are unique examples of structurally characterized actinide complexes with a BTBP molecule; this ligand adopts a planar conformation in the equatorial plane of the {UO2}2+ ion. In pyridine, 1 is dissociated into [UO2(OTf)2(py)3] and free CyMe4BTBP and the thermodynamic parameters (K, ΔH, ΔS) of this equilibrium have been determined by 1H NMR spectroscopy. The ethoxide derivative [UO2(OEt)(CyMe4BTBP)][OTf] (5) crystallized from a solution of 1 in a mixture of ethanol and acetone under air, and the dinuclear μ-oxo complex [{UO2(CyMe4BTBP)}2(μ-O)][I]2 (6) was obtained from [UO2I(thf)2.7] and CyMe4BTBP. The crystal structures of 6 and of the analogous derivatives [{UO2(py)4}2(μ-O)][I]2 (7) and [{UO2(TPTZ)(py)}2(μ-O)][I3]2 (8) exhibit a flexible [{UO2}–O–{UO2}]2+ moiety.

Keywords: Uranyl; Uranium; BTBP; Triflate; Iodide; Oxocompounds

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