Dispersion Forces Drive the Formation of Uranium–Alkane Adducts
[1];
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- Max-Planck Inst. for Kohlenforschung, Mülheim-an-der-Ruhr (Germany); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Friedrich-Alexander-Univ. Erlangen-Nürnberg (FAU) (Germany)
- Univ. Augsburg (Germany)
- Max-Planck Inst. for Chemical Energy Conversion, Mülheim-an-der-Ruhr (Germany)
- Max-Planck Inst. for Kohlenforschung, Mülheim-an-der-Ruhr (Germany)
- Max-Planck Inst. for Kohlenforschung, Mülheim-an-der-Ruhr (Germany); Bulgarian Academy of Sciences, Sofia (Bulgaria)
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 η2–H, C metal–alkane interactions in the [((t·BuArO)3tacn)UIII(Mecy-C6)]·(Mecy-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–OArO and U–Ntacn bonding parameters for the metal–tris(aryloxide) interaction. These parameters are incompatible with the concept of σ and π metal–ligand overlap. For that reason, it is deduced that metal–ligand bonding in the [((t·BuArO)3tacn)UIII] moiety is predominantly ionic. The bonding interaction within the [((t·BuArO)3tacn)UIII] moiety is shown to be dispersive in nature and essentially supported by the upper-rim tBu groups of the (t·BuArO)3tacn3– ligand. Finally, 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.
- Research Organization:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Organization:
- German Science Foundation; Max Planck Society; USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA)
- Grant/Contract Number:
- 89233218CNA000001
- OSTI ID:
- 1618322
- Report Number(s):
- LA-UR--19-22994
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 4 Vol. 142; ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
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