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Title: Periodic Trends in Actinyl Thio-Crown Ether Complexes

Abstract

In-cavity complexes and their bonding features between thio-crown (TC) ethers and f-elements are unexplored so far. In this paper, actinyl(VI) (An = U, Np, Pu, Am, and Cm) complexes of TC ethers have been characterized using relativistic density functional theory. The TC ether ligands include tetrathio-12-crown-4 (12TC4), pentathio-15-crown-5 (15TC5), and hexathio-18-crown-6 (18TC6). On the basis of the calculations, it is found that the "double-decker" sandwich structure of AnO2(12TC4)22+ and "side-on" structure AnO2(12TC4)2+ are changed to "insertion" structures for AnO2(15TC5)2+ and AnO2(18TC6)2+ due to increased size of the TC ether ligands. The actinyl monocyclic TC ether complexes are found to exhibit conventional conformations, with typical An-Oactinyl and An-Sliganddistances and angles. Chemical bonding analyses by Weinhold's natural population analysis (NPA), natural localized molecular orbital (NLMO), and energy decomposed analysis (EDA), show that a typical ionic An-Sligand bond with the extent of covalent interaction between the An and S atoms primarily attributable to the degree of radial distribution of the S 3p atomic orbitals. In conclusion, the similarity and difference of the oxo-crown and TC ethers as ligands for actinide coordination chemistry are discussed. As soft S-donor ligands, TC ethers may be candidate ligands for actinide recognition and extraction.

Authors:
 [1];  [2]; ORCiD logo [3]; ORCiD logo [2]
  1. Beijing Computational Science Research Center, Beijing (China); Tsinghua Univ., Beijing (China). Dept. of Chemistry and Key Lab. of Organic Optoelectronics & Molecular Engineering of Ministry of Education
  2. Tsinghua Univ., Beijing (China). Dept. of Chemistry and Key Lab. of Organic Optoelectronics & Molecular Engineering of Ministry of Education
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
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); National Natural Science Foundation of China (NSFC)
OSTI Identifier:
1461132
Grant/Contract Number:  
AC02-05CH11231; SC0016568; 21433005; 91426302; 21590792; 21701006
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 5; 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

Citation Formats

Hu, Shu-Xian, Liu, Jing-Jing, Gibson, John K., and Li, Jun. Periodic Trends in Actinyl Thio-Crown Ether Complexes. United States: N. p., 2018. Web. https://doi.org/10.1021/acs.inorgchem.7b03277.
Hu, Shu-Xian, Liu, Jing-Jing, Gibson, John K., & Li, Jun. Periodic Trends in Actinyl Thio-Crown Ether Complexes. United States. https://doi.org/10.1021/acs.inorgchem.7b03277
Hu, Shu-Xian, Liu, Jing-Jing, Gibson, John K., and Li, Jun. Mon . "Periodic Trends in Actinyl Thio-Crown Ether Complexes". United States. https://doi.org/10.1021/acs.inorgchem.7b03277. https://www.osti.gov/servlets/purl/1461132.
@article{osti_1461132,
title = {Periodic Trends in Actinyl Thio-Crown Ether Complexes},
author = {Hu, Shu-Xian and Liu, Jing-Jing and Gibson, John K. and Li, Jun},
abstractNote = {In-cavity complexes and their bonding features between thio-crown (TC) ethers and f-elements are unexplored so far. In this paper, actinyl(VI) (An = U, Np, Pu, Am, and Cm) complexes of TC ethers have been characterized using relativistic density functional theory. The TC ether ligands include tetrathio-12-crown-4 (12TC4), pentathio-15-crown-5 (15TC5), and hexathio-18-crown-6 (18TC6). On the basis of the calculations, it is found that the "double-decker" sandwich structure of AnO2(12TC4)22+ and "side-on" structure AnO2(12TC4)2+ are changed to "insertion" structures for AnO2(15TC5)2+ and AnO2(18TC6)2+ due to increased size of the TC ether ligands. The actinyl monocyclic TC ether complexes are found to exhibit conventional conformations, with typical An-Oactinyl and An-Sliganddistances and angles. Chemical bonding analyses by Weinhold's natural population analysis (NPA), natural localized molecular orbital (NLMO), and energy decomposed analysis (EDA), show that a typical ionic An-Sligand bond with the extent of covalent interaction between the An and S atoms primarily attributable to the degree of radial distribution of the S 3p atomic orbitals. In conclusion, the similarity and difference of the oxo-crown and TC ethers as ligands for actinide coordination chemistry are discussed. As soft S-donor ligands, TC ethers may be candidate ligands for actinide recognition and extraction.},
doi = {10.1021/acs.inorgchem.7b03277},
journal = {Inorganic Chemistry},
number = 5,
volume = 57,
place = {United States},
year = {2018},
month = {2}
}

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    Works referencing / citing this record:

    Theoretical studies on the oxidation states and electronic structures of actinide-borides: AnB 12 (An = Th–Cm) clusters
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