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Title: Cleaving Off Uranyl Oxygens through Chelation: A Mechanistic Study in the Gas Phase

Abstract

Recent efforts to activate the strong uranium-oxygen bonds in the dioxo uranyl cation have been limited to single oxo-group activation through either uranyl reduction and functionalization in solution, or by collision induced dissociation (CID) in the gas-phase, using mass spectrometry (MS). Here, we report and investigate the surprising double activation of uranyl by an organic ligand, 3,4,3-LI(CAM), leading to the formation of a formal U6+ chelate in the gas-phase. The cleavage of both uranyl oxo bonds was experimentally evidence d by CID, using deuterium and 18O isotopic substitutions, and by infrared multiple photon dissociation (IRMPD) spectroscopy. Density functional theory (DFT) computations predict that the overall reaction requires only 132 kJ/mol, with the first oxygen activation entailing about 107 kJ/mol. Here, combined with analysis of similar, but unreactive ligands, these results shed light on the chelation-driven mechanism of uranyl oxo bond cleavage, demonstrating its dependence on the presence of ligand hydroxyl protons available for direct interactions with the uranyl oxygens.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [1];  [1];  [1];  [1];  [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [1]
+ Show Author Affiliations
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Duquesne Univ., Pittsburgh, PA (United States)
  3. Radboud Univ., Nijmegen (The Netherlands)
  4. Radboud Univ., Nijmegen (The Netherlands); Univ. of Amsterdam, Amsterdam (The Netherlands)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1436648
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 56; Journal Issue: 21; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Uranyl activation; Actinide chemistry; Gas-phase chemistry; Collision induced dissociation; Uranium chelate

Citation Formats

Abergel, Rebecca J., de Jong, Wibe A., Deblonde, Gauthier J. -P., Dau, Phuong D., Captain, Ilya, Eaton, Teresa M., Jian, Jiwen, van Stipdonk, Michael J., Martens, Jonathan, Berden, Giel, Oomens, Jos, and Gibson, John K. Cleaving Off Uranyl Oxygens through Chelation: A Mechanistic Study in the Gas Phase. United States: N. p., 2017. Web. doi:10.1021/acs.inorgchem.7b01720.
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Abergel, Rebecca J., de Jong, Wibe A., Deblonde, Gauthier J. -P., Dau, Phuong D., Captain, Ilya, Eaton, Teresa M., Jian, Jiwen, van Stipdonk, Michael J., Martens, Jonathan, Berden, Giel, Oomens, Jos, & Gibson, John K. Cleaving Off Uranyl Oxygens through Chelation: A Mechanistic Study in the Gas Phase. United States. https://doi.org/10.1021/acs.inorgchem.7b01720
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Abergel, Rebecca J., de Jong, Wibe A., Deblonde, Gauthier J. -P., Dau, Phuong D., Captain, Ilya, Eaton, Teresa M., Jian, Jiwen, van Stipdonk, Michael J., Martens, Jonathan, Berden, Giel, Oomens, Jos, and Gibson, John K. Wed . "Cleaving Off Uranyl Oxygens through Chelation: A Mechanistic Study in the Gas Phase". United States. https://doi.org/10.1021/acs.inorgchem.7b01720. https://www.osti.gov/servlets/purl/1436648.
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@article{osti_1436648,
title = {Cleaving Off Uranyl Oxygens through Chelation: A Mechanistic Study in the Gas Phase},
author = {Abergel, Rebecca J. and de Jong, Wibe A. and Deblonde, Gauthier J. -P. and Dau, Phuong D. and Captain, Ilya and Eaton, Teresa M. and Jian, Jiwen and van Stipdonk, Michael J. and Martens, Jonathan and Berden, Giel and Oomens, Jos and Gibson, John K.},
abstractNote = {Recent efforts to activate the strong uranium-oxygen bonds in the dioxo uranyl cation have been limited to single oxo-group activation through either uranyl reduction and functionalization in solution, or by collision induced dissociation (CID) in the gas-phase, using mass spectrometry (MS). Here, we report and investigate the surprising double activation of uranyl by an organic ligand, 3,4,3-LI(CAM), leading to the formation of a formal U6+ chelate in the gas-phase. The cleavage of both uranyl oxo bonds was experimentally evidence d by CID, using deuterium and 18O isotopic substitutions, and by infrared multiple photon dissociation (IRMPD) spectroscopy. Density functional theory (DFT) computations predict that the overall reaction requires only 132 kJ/mol, with the first oxygen activation entailing about 107 kJ/mol. Here, combined with analysis of similar, but unreactive ligands, these results shed light on the chelation-driven mechanism of uranyl oxo bond cleavage, demonstrating its dependence on the presence of ligand hydroxyl protons available for direct interactions with the uranyl oxygens.},
doi = {10.1021/acs.inorgchem.7b01720},
journal = {Inorganic Chemistry},
number = 21,
volume = 56,
place = {United States},
year = {Wed Oct 11 00:00:00 EDT 2017},
month = {Wed Oct 11 00:00:00 EDT 2017}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.inorgchem.7b01720
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Cited by: 18 works
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Figures / Tables:

Figure 1 Figure 1: (top) CID ESI-MS spectra of [UO2(CAMH7)]- (blue) and [UO2(CAMD7)]- (red). Nominal CID voltage = 0.25 V. (bottom) CID ESI-MS spectrum of the ligand CAMH9-. Nominal CID voltage = 0.70 V. The structures of the ligand (CAMH10) and its deuterated version (CAMD10) are given for clarity. The dominant fragmentationmore » pathways are two H2O losses for [UO2(CAMH7)]- and two D2O losses for [UO2(CAMD7)]-; water loss is not observed for CAMH9-. Also observed are ligand cleavages as indicated, concomitant with H-atom transfer from the eliminated neutral fragment (136 m/z); this is the only pathway observed for the ligand. Although the fragmentation mechanisms are not revealed by these results, the peaks at 859, 841, and 824 m/z correspond to the respective losses of “136” and one H2O; “136” and two H2O; and “136”, two H2O, and one OH from [UO2(CAMH7)]-.« less
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    Works referencing / citing this record:

    Ligand‐Supported Facile Conversion of Uranyl(VI) into Uranium(IV) in Organic and Aqueous Media
    journal, February 2020

    • Faizova, Radmila; Fadaei‐Tirani, Farzaneh; Bernier‐Latmani, Rizlan
    • Angewandte Chemie International Edition, Vol. 59, Issue 17
    • DOI: 10.1002/anie.201916334

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    Ligand‐Supported Facile Conversion of Uranyl(VI) into Uranium(IV) in Organic and Aqueous Media
    journal, April 2020

    • Faizova, Radmila; Fadaei‐Tirani, Farzaneh; Bernier‐Latmani, Rizlan
    • Angewandte Chemie, Vol. 132, Issue 17
    • DOI: 10.1002/ange.201916334
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