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Oxidation state delineation via U L III-edge XANES in a series of isostructural uranium coordination complexes

Kosog B, la Pierre HS, Denecke MA, Heinemann FW, Meyer K (2012)

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Publication Type: Journal article, Original article

Publication year: 2012

Journal

Original Authors: Kosog B., La Pierre H.S., Denecke M.A., Heinemann F.W., Meyer K.

Publisher: American Chemical Society

Book Volume: 51

Pages Range: 7940-7944

Journal Issue: 14

DOI: 10.1021/ic3011234

Abstract

We present an X-ray absorption near-edge structure (XANES) study of a series of uranium coordination complexes that possess nearly identical first coordination spheres and geometries in a range of oxidation states from U to U . These compounds were obtained through the activation of small molecules, such as ketones, azides, and carbon dioxide, and upon oxidation of a high-valent U ≡O to [U ≡ O] . Most of the compounds have been reported previously. All of them are fully characterized and their oxidation states have been confirmed by various spectroscopic methods (SQUID, H NMR, and UV/vis/near-IR). Each uranium complex consists of a triazacyclononane anchor bearing three aryloxide side arms with bulky tert-butyl (t-Bu) or adamantyl (Ad) ortho substituents. All complexes have approximate C symmetry and possess an axial cavity that is either empty (U ) or occupied by a seventh ligand, namely, terminal oxygen (U and U ) or an oxygen-containing ligand (U ). The only exception is [(( ArO) tacnU (O)][SbF ], which is the rare case of a complex that shows a strong inverse trans influence. The determined correlation between the uranium oxidation state and the U L -edge XANES absorption in this series includes a single terminal oxo ligand bonded uranium(V,VI), for which data are essentially nonexistent. The correct assignment of the uranium valence in a U -L compound (L = ketyl radical) is shown to be only possible by a comparison to structurally similar compounds. © 2012 American Chemical Society.

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How to cite

APA:

Kosog, B., la Pierre, H.S., Denecke, M.A., Heinemann, F.W., & Meyer, K. (2012). Oxidation state delineation via U L III-edge XANES in a series of isostructural uranium coordination complexes. Inorganic Chemistry, 51(14), 7940-7944. https://doi.org/10.1021/ic3011234

MLA:

Kosog, Boris, et al. "Oxidation state delineation via U L III-edge XANES in a series of isostructural uranium coordination complexes." Inorganic Chemistry 51.14 (2012): 7940-7944.

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