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Dispersion Forces Drive the Formation of Uranium-Alkane Adducts

MPS-Authors
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Jung,  Julie
Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society;
Theory, Fritz Haber Institute, Max Planck Society;

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Bill,  Eckhard
Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Bistoni,  Giovanni
Research Group Bistoni, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Atanasov,  Mihail
Research Group Atanasov, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Neese,  Frank
Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society;
Institut für Physikalische und Theoretische Chemie, Universität Bonn, Wegelerstrasse 12, D-53115 Bonn, Germany;

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Citation

Jung, J., Löffler, S. T., Langmann, J., Heinemann, F. W., Bill, E., Bistoni, G., et al. (2020). Dispersion Forces Drive the Formation of Uranium-Alkane Adducts. Journal of the American Chemical Society, 142(4), 1864-1870. doi:10.1021/jacs.9b10620.


Cite as: http://hdl.handle.net/21.11116/0000-0007-B394-7
Abstract
Single-crystal cryogenic X-ray diffraction at 6 K, electron paramagnetic resonance spectroscopy, and correlated electronic structure calculations are combined to shed light on the nature of the metal-tris(aryloxide) and eta(2)-H, C metal-alkane interactions in the [(((ArO)-Ar-t center dot Bu)(3)tacn)U-III((me)cy-C6)]center dot((me)cy-C6) adduct. An analysis of the ligand field experienced by the uranium center using ab initio ligand field theory in combination with the angular overlap model yields rather unusual U-O-ArO and U-N-tacn bonding parameters for the metal-tris(aryloxide) interaction. These parameters are incompatible with the concept of sigma and pi metal-ligand overlap. For that reason, it is deduced that metal-ligand bonding in the [(((ArO)-Ar-t center dot Bu)(3)tacn)U-III] moiety is predominantly ionic. The bonding interaction within the [(((ArO)-Ar-t center dot Bu)(3)tacn)-U-III] moiety is shown to be dispersive in nature and essentially supported by the upper-rim Bu-t groups of the ((ArO)-Ar-t center dot Bu)(3)tacn(3)-ligand. Our findings indicate that the axial alkane molecule is held in place by the guest-host effect rather than direct metal-alkane ionic or covalent interactions.