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Title: Destruction of the Uranyl Moiety in a U(V) “Cation–Cation” Interaction

Abstract

A gas-phase uranyl peroxide dimer supported by three 12-crown-4 ether (12C4) ligands, [(UO2)2(O2)(12C4)3)]2+ (A), was prepared by electrospray ionization. Density functional theory (DFT) indicates a structure with two terminal 12C4 and the third 12C4 bridging the uranium centers. Collision induced dissociation (CID) of A resulted in elimination of the bridging 12C4 to yield a uranyl peroxide dimer with two terminal donor ligands, [(12C4)(UO2)(O2)(UO2)(12C4)]2+ (B). Remarkably, CID of B resulted in elimination of the bridging peroxide concomitant with reduction of U(VI) to U(V) in C, [(12C4)(UO2)(UO2)(12C4)]2+. DFT studies indicate that in C there is direct interaction between the two UO2+ species, which can thus be considered as a so-called cation-cation interaction (CCI). This formal CCI, induced by tetradentate 12C4 ligands, corresponds to destruction of the linear uranyl moieties and creation of bridging U-O-U oxo-bonds. Finally, on the basis of the structural rearrangement to achieve the structurally extreme CCI interaction, it is predicted also to be accessible for PaO2+ but is less feasible for transuranic actinyls.

Authors:
 [1];  [2];  [3]; ORCiD logo [2]
  1. Beijing Computational Science Research Center (China); Tsinghua Univ., Beijing (China)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Tsinghua Univ., Beijing (China); Southern Univ. of Science and Technology, Shenzhen (China)
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); NASF; National Natural Science Foundation of China (NSFC)
OSTI Identifier:
1631606
Grant/Contract Number:  
AC02-05CH11231; SC0016568; U1530401; YZJJSQ2017072; 91426302; 21433005; 21701006
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 58; Journal Issue: 15; 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; chemical structure; oxides; energy; ligands; cations

Citation Formats

Hu, Shu-Xian, Jian, Jiwen, Li, Jun, and Gibson, John K. Destruction of the Uranyl Moiety in a U(V) “Cation–Cation” Interaction. United States: N. p., 2019. Web. doi:10.1021/acs.inorgchem.9b01265.
Hu, Shu-Xian, Jian, Jiwen, Li, Jun, & Gibson, John K. Destruction of the Uranyl Moiety in a U(V) “Cation–Cation” Interaction. United States. https://doi.org/10.1021/acs.inorgchem.9b01265
Hu, Shu-Xian, Jian, Jiwen, Li, Jun, and Gibson, John K. Thu . "Destruction of the Uranyl Moiety in a U(V) “Cation–Cation” Interaction". United States. https://doi.org/10.1021/acs.inorgchem.9b01265. https://www.osti.gov/servlets/purl/1631606.
@article{osti_1631606,
title = {Destruction of the Uranyl Moiety in a U(V) “Cation–Cation” Interaction},
author = {Hu, Shu-Xian and Jian, Jiwen and Li, Jun and Gibson, John K.},
abstractNote = {A gas-phase uranyl peroxide dimer supported by three 12-crown-4 ether (12C4) ligands, [(UO2)2(O2)(12C4)3)]2+ (A), was prepared by electrospray ionization. Density functional theory (DFT) indicates a structure with two terminal 12C4 and the third 12C4 bridging the uranium centers. Collision induced dissociation (CID) of A resulted in elimination of the bridging 12C4 to yield a uranyl peroxide dimer with two terminal donor ligands, [(12C4)(UO2)(O2)(UO2)(12C4)]2+ (B). Remarkably, CID of B resulted in elimination of the bridging peroxide concomitant with reduction of U(VI) to U(V) in C, [(12C4)(UO2)(UO2)(12C4)]2+. DFT studies indicate that in C there is direct interaction between the two UO2+ species, which can thus be considered as a so-called cation-cation interaction (CCI). This formal CCI, induced by tetradentate 12C4 ligands, corresponds to destruction of the linear uranyl moieties and creation of bridging U-O-U oxo-bonds. Finally, on the basis of the structural rearrangement to achieve the structurally extreme CCI interaction, it is predicted also to be accessible for PaO2+ but is less feasible for transuranic actinyls.},
doi = {10.1021/acs.inorgchem.9b01265},
journal = {Inorganic Chemistry},
number = 15,
volume = 58,
place = {United States},
year = {2019},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
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Figures / Tables:

Scheme 1 Scheme 1: Possible types of cation-cation interaction between two UO2 +.

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Works referenced in this record:

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