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Title: Synthesis, Structure, and Vibrational Properties of [Ph4P]2NpO2Cl4 and [Ph4P]2PuO2Cl4 Complexes

Abstract

In this paper, the synthesis, structure, and vibrational properties are presented for an isostructural series of Np(VI) and Pu(VI) complexes of the form [Ph4P]2AnO2Cl4, where An = Np(VI) or Pu(VI). The reported complexes are readily synthesized in ambient laboratory conditions, and their molecular structures were determined using single crystal X-ray diffraction. Their vibrational spectra were studied using a combination of Raman and FT-IR vibrational spectroscopies. Analysis of the vibrational spectra and force constants highlight the periodic properties associated with the actinide contraction and filling of the 5f electronic shells. Finally and additionally, we have assessed the utility of these complexes as conveniently synthesized starting materials for non-aqueous synthesis of transuranium molecules and materials.

Authors:
 [1]; ORCiD logo [1]
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  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1461426
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 6; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Schnaars, David D., and Wilson, Richard E.. Synthesis, Structure, and Vibrational Properties of [Ph4P]2NpO2Cl4 and [Ph4P]2PuO2Cl4 Complexes. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.7b02382.
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Schnaars, David D., & Wilson, Richard E.. Synthesis, Structure, and Vibrational Properties of [Ph4P]2NpO2Cl4 and [Ph4P]2PuO2Cl4 Complexes. United States. https://doi.org/10.1021/acs.inorgchem.7b02382
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Schnaars, David D., and Wilson, Richard E.. Thu . "Synthesis, Structure, and Vibrational Properties of [Ph4P]2NpO2Cl4 and [Ph4P]2PuO2Cl4 Complexes". United States. https://doi.org/10.1021/acs.inorgchem.7b02382. https://www.osti.gov/servlets/purl/1461426.
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@article{osti_1461426,
title = {Synthesis, Structure, and Vibrational Properties of [Ph4P]2NpO2Cl4 and [Ph4P]2PuO2Cl4 Complexes},
author = {Schnaars, David D. and Wilson, Richard E.},
abstractNote = {In this paper, the synthesis, structure, and vibrational properties are presented for an isostructural series of Np(VI) and Pu(VI) complexes of the form [Ph4P]2AnO2Cl4, where An = Np(VI) or Pu(VI). The reported complexes are readily synthesized in ambient laboratory conditions, and their molecular structures were determined using single crystal X-ray diffraction. Their vibrational spectra were studied using a combination of Raman and FT-IR vibrational spectroscopies. Analysis of the vibrational spectra and force constants highlight the periodic properties associated with the actinide contraction and filling of the 5f electronic shells. Finally and additionally, we have assessed the utility of these complexes as conveniently synthesized starting materials for non-aqueous synthesis of transuranium molecules and materials.},
doi = {10.1021/acs.inorgchem.7b02382},
journal = {Inorganic Chemistry},
number = 6,
volume = 57,
place = {United States},
year = {2018},
month = {3}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1021/acs.inorgchem.7b02382
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Cited by: 15 works
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Figures / Tables:

Figure 1 Figure 1: Solid-state structures of [PPh4]2NpO2Cl4·2CH2Cl2 Np in gray, chlorine (green), oxygen (red), phosphorous (magenta), carbon (black). H atoms on the PPh4+ cation have been omitted for clarity.
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    Works referencing / citing this record:

    Impacts of hydrogen bonding interactions with Np( v / vi )O 2 Cl 4 complexes: vibrational spectroscopy, redox behavior, and computational analysis
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    • DOI: 10.1002/chem.201801044
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      Figure 1 (p. 23)figure
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      Figure 3 (p. 25)figure
      Table 1 (p. 27)table
      Table 2 (p. 28)table
      Table 3 (p. 29)table
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