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Redox properties of biscyclopentadienyl uranium(V) imido-halide complexes: a relativistic DFT study

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Abstract

Calculations of ionization energies (IE) and electron affinities (EA) of a series of biscyclopentadienyl imido-halide uranium(V) complexes Cp* 2 U(=N–2,6– i Pr 2 –C 6 H 3 )(X) with X = F, Cl, Br, and I, related to the UIV/UV and UV/UVI redox systems, were carried out, for the first time, using density functional theory (DFT) in the framework of the relativistic zeroth order regular approximation (ZORA) coupled with the conductor-like screening model (COSMO) solvation approach. A very good linear correlation (R 2 = 0.993) was obtained, between calculated ionization energies at the ZORA/BP86/TZP level, and the experimental half-wave oxidation potentials E 1/2. A similar linear correlation between the computed electron affinities and the electrochemical reduction UIV/UIII potentials (R 2 = 0.996) is obtained. The importance of solvent effects and of spin-orbit coupling is definitively confirmed. The molecular orbital analysis underlines the crucial role played by the 5f orbitals of the central metal whereas the Nalewajski-Mrozek (N–M) bond indices explain well the bond distances variations following the redox processes. The IE variation of the complexes, i.e., IE(F) < IE(Cl) < IE(Br) < IE(I) is also well rationalized considering the frontier MO diagrams of these species. Finally, this work confirms the relevance of the Hirshfeld charges analysis which bring to light an excellent linear correlation (R 2 = 0.999) between the variations of the uranium charges and E 1/2 in the reduction process of the UV species.

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Acknowledgments

The authors acknowledge the financial support from the Algerian Project CNEPRU n° D00520130051. Computing facilities were provided by GENCI-IDRIS and GENCI-CINES. The COST CM-1006 action is also acknowledged.

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Authors and Affiliations

  1. Laboratoire de Physique et Chimie Quantique, Faculté des Sciences, Université Mouloud Mammeri, 15000, Tizi-Ouzou, Algeria

    Aziz Elkechai, Farida Kias & Fazia Talbi

  2. Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, 35042, Rennes Cedex, France

    Abdou Boucekkine

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  1. Aziz Elkechai
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  2. Farida Kias
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  3. Fazia Talbi
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  4. Abdou Boucekkine
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Correspondence to Abdou Boucekkine.

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This paper belongs to Topical Collection QUITEL 2013

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Elkechai, A., Kias, F., Talbi, F. et al. Redox properties of biscyclopentadienyl uranium(V) imido-halide complexes: a relativistic DFT study. J Mol Model 20, 2294 (2014). https://doi.org/10.1007/s00894-014-2294-5

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