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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]
+ Show Author Affiliations
  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. doi:10.1016/j.jorganchem.2017.10.010.
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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
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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.
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@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 = {Sat Oct 14 00:00:00 EDT 2017},
month = {Sat Oct 14 00:00:00 EDT 2017}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1016/j.jorganchem.2017.10.010
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Cited by: 6 works
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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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Works referenced in this record:

Electronic Structure, Spectra, and Magnetic Properties of Oxycations. III. Ligation Effects on the Infrared Spectrum of the Uranyl Ion
journal, July 1961

  • McGlynn, S. P.; Smith, J. K.; Neely, W. C.
  • The Journal of Chemical Physics, Vol. 35, Issue 1
  • DOI: 10.1063/1.1731876

The Raman Scattering of Uranyl and Transuranium V, VI, and VII Ions
journal, March 1974

Aqueous uranium complexes. 2. Raman spectroscopic study of the complex formation of the dioxouranium(VI) ion with a variety of inorganic and organic ligands
journal, December 1992

  • Nguyen Trung, Chinh; Begun, G. M.; Palmer, Donald A.
  • Inorganic Chemistry, Vol. 31, Issue 25
  • DOI: 10.1021/ic00051a021

Distorted Equatorial Coordination Environments and Weakening of UO Bonds in Uranyl Complexes Containing NCN and NPN Ligands
journal, May 2004

  • Sarsfield, Mark J.; Helliwell, Madeleine; Raftery, James
  • Inorganic Chemistry, Vol. 43, Issue 10
  • DOI: 10.1021/ic035349c

Lattice Solvent and Crystal Phase Effects on the Vibrational Spectra of UO 2 Cl 4 2–
journal, September 2014

  • Schnaars, David D.; Wilson, Richard E.
  • Inorganic Chemistry, Vol. 53, Issue 20
  • DOI: 10.1021/ic501553m

Vibrational Spectroscopy of Mass-Selected [UO 2 (ligand) n ] 2+ Complexes in the Gas Phase:  Comparison with Theory
journal, April 2006

  • Groenewold, Gary S.; Gianotto, Anita K.; Cossel, Kevin C.
  • Journal of the American Chemical Society, Vol. 128, Issue 14
  • DOI: 10.1021/ja058106n

Gas-phase basicities of polyfunctional molecules. Part 2: Saturated basic sites: POLYFUNCTIONAL MOLECULES WITH SATURATED BASIC SITES
journal, July 2011

  • Bouchoux, Guy; Salpin, Jean-Yves
  • Mass Spectrometry Reviews, Vol. 31, Issue 3
  • DOI: 10.1002/mas.20343

The nature of the bonding of Li+ to H2O and NH3; A3 initio studies
journal, June 1976

Revised and Expanded Scale of Gas-Phase Lithium Cation Basicities. An Experimental and Theoretical Study
journal, March 2000

  • Burk, Peeter; Koppel, Ilmar A.; Koppel, Ivar
  • The Journal of Physical Chemistry A, Vol. 104, Issue 12
  • DOI: 10.1021/jp9931399

An Experimental and Ab Initio Study of the Nature of the Binding in Gas-Phase Complexes of Sodium Ions
journal, August 2000

Infrared Multiphoton Dissociation Spectroscopy of a Gas-Phase Complex of Uranyl and 3-Oxa-Glutaramide: An Extreme Red-Shift of the [O═U═O] 2+ Asymmetric Stretch
journal, March 2015

  • Gibson, John K.; Hu, Han-Shi; Van Stipdonk, Michael J.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 14
  • DOI: 10.1021/jp512599e

Electronic structure and characterization of a uranyl di-15-crown-5 complex with an unprecedented sandwich structure
journal, January 2016

  • Hu, Shu-Xian; Gibson, John K.; Li, Wan-Lu
  • Chemical Communications, Vol. 52, Issue 86
  • DOI: 10.1039/C6CC07205D

Free electron laser-Fourier transform ion cyclotron resonance mass spectrometry facility for obtaining infrared multiphoton dissociation spectra of gaseous ions
journal, February 2005

  • Valle, Jose J.; Eyler, John R.; Oomens, Jos
  • Review of Scientific Instruments, Vol. 76, Issue 2
  • DOI: 10.1063/1.1841953

Laboratory Infrared Spectroscopy of Cationic Polycyclic Aromatic Hydrocarbon Molecules
journal, July 2003

  • Oomens, Jos; Tielens, A. G. G. M.; Sartakov, Boris G.
  • The Astrophysical Journal, Vol. 591, Issue 2
  • DOI: 10.1086/375515

Vibrational Characterization of Simple Peptides Using Cryogenic Infrared Photodissociation of H 2 -Tagged, Mass-Selected Ions
journal, April 2011

  • Kamrath, Michael Z.; Garand, Etienne; Jordan, Peter A.
  • Journal of the American Chemical Society, Vol. 133, Issue 16
  • DOI: 10.1021/ja200849g

Interaction of Cu + with cytosine and formation of i-motif-like C–M + –C complexes: alkali versus coinage metals
journal, January 2016

  • Gao, Juehan; Berden, Giel; Rodgers, M. T.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 10
  • DOI: 10.1039/C6CP00234J

NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010

  • Valiev, M.; Bylaska, E. J.; Govind, N.
  • Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
  • DOI: 10.1016/j.cpc.2010.04.018

Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis
journal, August 1980

  • Vosko, S. H.; Wilk, L.; Nusair, M.
  • Canadian Journal of Physics, Vol. 58, Issue 8
  • DOI: 10.1139/p80-159

A new mixing of Hartree–Fock and local density‐functional theories
journal, January 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 2
  • DOI: 10.1063/1.464304

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988

Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide
journal, May 1994

  • Küchle, W.; Dolg, M.; Stoll, H.
  • The Journal of Chemical Physics, Vol. 100, Issue 10
  • DOI: 10.1063/1.466847

Optimization of Gaussian-type basis sets for local spin density functional calculations. Part I. Boron through neon, optimization technique and validation
journal, February 1992

  • Godbout, Nathalie; Salahub, Dennis R.; Andzelm, Jan
  • Canadian Journal of Chemistry, Vol. 70, Issue 2
  • DOI: 10.1139/v92-079

Comparison between Optimized Geometries and Vibrational Frequencies Calculated by the DFT Methods
journal, January 1996

  • El-Azhary, A. A.; Suter, H. U.
  • The Journal of Physical Chemistry, Vol. 100, Issue 37
  • DOI: 10.1021/jp960618o

Evaluated Gas Phase Basicities and Proton Affinities of Molecules: An Update
journal, May 1998

  • Hunter, Edward P. L.; Lias, Sharon G.
  • Journal of Physical and Chemical Reference Data, Vol. 27, Issue 3
  • DOI: 10.1063/1.556018

Proton affinity of deuterated acetonitrile estimated by the kinetic method with full entropy analysis
journal, September 2001

  • Williams, Taufika Islam; Denault, Jeff W.; Cooks, R. Graham
  • International Journal of Mass Spectrometry, Vol. 210-211
  • DOI: 10.1016/S1387-3806(01)00455-9

Proton affinity determinations using the kinetic method in an ion trap mass spectrometer
journal, May 1991

  • Nourse, Bobette D.; Graham Cooks, R.
  • International Journal of Mass Spectrometry and Ion Processes, Vol. 106
  • DOI: 10.1016/0168-1176(91)85022-E

Thiocarbonyl versus carbonyl compounds: A comparison of intrinsic reactivities
journal, December 1993

  • Abboud, J. L. M.; Mo, O.; de Paz, J. L. G.
  • Journal of the American Chemical Society, Vol. 115, Issue 26
  • DOI: 10.1021/ja00079a030

Chemistry is about energy and its changes: A critique of bond-length/bond-strength correlations
journal, August 2017

Gas-Phase Energetics of Actinide Oxides: An Assessment of Neutral and Cationic Monoxides and Dioxides from Thorium to Curium †
journal, November 2009

  • Marçalo, Joaquim; Gibson, John K.
  • The Journal of Physical Chemistry A, Vol. 113, Issue 45
  • DOI: 10.1021/jp904862a

Protonation of polyethers, glymes, and crown ethers in the gas phase
journal, February 1984

  • Sharma, Ram B.; Blades, Arthur T.; Kebarle, Paul
  • Journal of the American Chemical Society, Vol. 106, Issue 3
  • DOI: 10.1021/ja00315a007
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