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Title: Equatorial coordination of uranyl: Correlating ligand charge donation with the Oyl-U-Oyl asymmetric stretch frequency

Abstract

In uranyl coordination complexes, UO2(L)n2+, uranium in the formally dipositive [O=U=O]2+ moiety is coordinated by n neutral organic electron donor ligands, L. The extent of ligand electron donation, which results in partial reduction of uranyl and weakening of the U=O bonds, is revealed by the magnitude of the red-shift of the uranyl asymmetric stretch frequency, ν3 . This phenomenon appears in gas-phase complexes in which uranyl is coordinated by electron donor ligands: the ν3 red-shift increases as the number of ligands and their proton affinity (PA) increases. Because PA is a measure of the enthalpy change associated with a proton-ligand interaction, which is much stronger and of a different nature than metal ion-ligand bonding, it is not necessarily expected that ligand PAs should reliably predict uranyl-ligand bonding and the resulting ν3 red-shift. In this study, ν3 was measured for uranyl coordinated by ligands with a relatively broad range of PAs, revealing a surprisingly good correlation between PA and ν3 frequency. From computed ν3 frequencies for bare UO2 cations and neutrals, it is inferred that the effective charge of uranyl in UO2(L)n2+ complexes can be reduced to near zero upon ligation by sufficiently strong charge-donor ligands. The basis for the correlationmore » between ν3 and ligand PAs, as well as limitations and deviations from it, are considered. It is demonstrated that the correlation evidently extends to a ligand that exhibits polydentate metal ion coordination.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [4];  [4];  [5]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Computational Research Division
  3. Duquesne Univ., Pittsburgh, PA (United States). Dept. of Chemistry and Biochemistry
  4. Radboud Univ., Nijmegen (Netherlands). Inst. for Molecules and Materials and FELIX Lab.
  5. Radboud Univ., Nijmegen (Netherlands). Inst. for Molecules and Materials and FELIX Lab.; Univ. of Amsterdam (Netherlands). Van‘t Hoff Inst. for Molecular Sciences (HIMS)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Actinide Science & Technology (CAST); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; Duquesne Univ., Pittsburgh, PA (United States); Netherlands Organisation for Scientific Research (NWO); Innovative and Novel Computational Impact on Theory and Experiment (INCITE)
OSTI Identifier:
1436668
Alternate Identifier(s):
OSTI ID: 1549465
Grant/Contract Number:  
AC02-05CH11231; SC0016568; 724.011.002; AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Organometallic Chemistry
Additional Journal Information:
Journal Volume: 857; Journal Issue: C; Journal ID: ISSN 0022-328X
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; Uranyl; Coordination complexes: gas-phase; IRMPD; Proton affinity

Citation Formats

Gibson, John K., de Jong, Wibe A., van Stipdonk, Michael J., Martens, Jonathan, Berden, Giel, and Oomens, Jos. Equatorial coordination of uranyl: Correlating ligand charge donation with the Oyl-U-Oyl asymmetric stretch frequency. United States: N. p., 2017. Web. https://doi.org/10.1016/j.jorganchem.2017.10.010.
Gibson, John K., de Jong, Wibe A., van Stipdonk, Michael J., Martens, Jonathan, Berden, Giel, & Oomens, Jos. Equatorial coordination of uranyl: Correlating ligand charge donation with the Oyl-U-Oyl asymmetric stretch frequency. United States. https://doi.org/10.1016/j.jorganchem.2017.10.010
Gibson, John K., de Jong, Wibe A., van Stipdonk, Michael J., Martens, Jonathan, Berden, Giel, and Oomens, Jos. Sat . "Equatorial coordination of uranyl: Correlating ligand charge donation with the Oyl-U-Oyl asymmetric stretch frequency". United States. https://doi.org/10.1016/j.jorganchem.2017.10.010. https://www.osti.gov/servlets/purl/1436668.
@article{osti_1436668,
title = {Equatorial coordination of uranyl: Correlating ligand charge donation with the Oyl-U-Oyl asymmetric stretch frequency},
author = {Gibson, John K. and de Jong, Wibe A. and van Stipdonk, Michael J. and Martens, Jonathan and Berden, Giel and Oomens, Jos},
abstractNote = {In uranyl coordination complexes, UO2(L)n2+, uranium in the formally dipositive [O=U=O]2+ moiety is coordinated by n neutral organic electron donor ligands, L. The extent of ligand electron donation, which results in partial reduction of uranyl and weakening of the U=O bonds, is revealed by the magnitude of the red-shift of the uranyl asymmetric stretch frequency, ν3 . This phenomenon appears in gas-phase complexes in which uranyl is coordinated by electron donor ligands: the ν3 red-shift increases as the number of ligands and their proton affinity (PA) increases. Because PA is a measure of the enthalpy change associated with a proton-ligand interaction, which is much stronger and of a different nature than metal ion-ligand bonding, it is not necessarily expected that ligand PAs should reliably predict uranyl-ligand bonding and the resulting ν3 red-shift. In this study, ν3 was measured for uranyl coordinated by ligands with a relatively broad range of PAs, revealing a surprisingly good correlation between PA and ν3 frequency. From computed ν3 frequencies for bare UO2 cations and neutrals, it is inferred that the effective charge of uranyl in UO2(L)n2+ complexes can be reduced to near zero upon ligation by sufficiently strong charge-donor ligands. The basis for the correlation between ν3 and ligand PAs, as well as limitations and deviations from it, are considered. It is demonstrated that the correlation evidently extends to a ligand that exhibits polydentate metal ion coordination.},
doi = {10.1016/j.jorganchem.2017.10.010},
journal = {Journal of Organometallic Chemistry},
number = C,
volume = 857,
place = {United States},
year = {2017},
month = {10}
}

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Figures / Tables:

Table 1 Table 1: Experimental and computed (LDA and B3LYP functional) ѵ3 frequencies (cm-1) for UO2(L)32+ complexes, and ligand L proton affinities (kJ/mol).

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.