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Title: Synthesis and Crystal Structures of Volatile Neptunium(IV) β-Diketonates

Abstract

There is a large need for neptunium certified reference materials to support domestic nuclear forensics programs. These reference materials are required for quantification of Np forensic related samples. Isotopic separation is required to produce this material; traditional isotopic separation methods use electromagnetic separation techniques. Such methods require a gaseous introduction of Np into the separation source. This work sought to produce a volatile Np compound that would be suitable for the purpose of certified reference material production. ß-diketonates were identified as compounds likely able to serve this purpose. However, previously described synthesis requires NpCl4, which is not commercially available and prohibitively difficult to produce. A novel and facile procedure was developed here to successfully synthesize several tetravalent ß-diketonates of Np. They were characterized using FTIR and single crystal x-ray diffraction. The volatility of these compounds at elevated temperatures was then analyzed, and discussed. The synthesis procedure developed here presents a facile platform for further Np organometallic studies.

Authors:
ORCiD logo [1];  [2];  [2]; ORCiD logo [1];  [3];  [2];  [2]; ORCiD logo [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Idaho National Lab. (INL), Idaho Falls, ID (United States)
  2. Washington State Univ., Pullman, WA (United States)
  3. Univ. of Notre Dame, Notre Dame, IN (United States)
Publication Date:
Research Org.:
Idaho National Laboratory (INL), Idaho Falls, ID (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1478397
Report Number(s):
INL/JOU-16-40633-Rev000
Journal ID: ISSN 0020-1669
Grant/Contract Number:  
AC07-05ID14517
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; Neptunium; Volatile; Diketone

Citation Formats

Johnson, Aaron T., Parker, T. Gannon, Dickens, Sara M., Pfeiffer, Jana K., Oliver, Allen G., Wall, Donald, Wall, Nathalie A., Finck, Martha R., and Carney, Kevin P. Synthesis and Crystal Structures of Volatile Neptunium(IV) β-Diketonates. United States: N. p., 2017. Web. doi:10.1021/acs.inorgchem.7b02290.
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Johnson, Aaron T., Parker, T. Gannon, Dickens, Sara M., Pfeiffer, Jana K., Oliver, Allen G., Wall, Donald, Wall, Nathalie A., Finck, Martha R., & Carney, Kevin P. Synthesis and Crystal Structures of Volatile Neptunium(IV) β-Diketonates. United States. https://doi.org/10.1021/acs.inorgchem.7b02290
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Johnson, Aaron T., Parker, T. Gannon, Dickens, Sara M., Pfeiffer, Jana K., Oliver, Allen G., Wall, Donald, Wall, Nathalie A., Finck, Martha R., and Carney, Kevin P. Tue . "Synthesis and Crystal Structures of Volatile Neptunium(IV) β-Diketonates". United States. https://doi.org/10.1021/acs.inorgchem.7b02290. https://www.osti.gov/servlets/purl/1478397.
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@article{osti_1478397,
title = {Synthesis and Crystal Structures of Volatile Neptunium(IV) β-Diketonates},
author = {Johnson, Aaron T. and Parker, T. Gannon and Dickens, Sara M. and Pfeiffer, Jana K. and Oliver, Allen G. and Wall, Donald and Wall, Nathalie A. and Finck, Martha R. and Carney, Kevin P.},
abstractNote = {There is a large need for neptunium certified reference materials to support domestic nuclear forensics programs. These reference materials are required for quantification of Np forensic related samples. Isotopic separation is required to produce this material; traditional isotopic separation methods use electromagnetic separation techniques. Such methods require a gaseous introduction of Np into the separation source. This work sought to produce a volatile Np compound that would be suitable for the purpose of certified reference material production. ß-diketonates were identified as compounds likely able to serve this purpose. However, previously described synthesis requires NpCl4, which is not commercially available and prohibitively difficult to produce. A novel and facile procedure was developed here to successfully synthesize several tetravalent ß-diketonates of Np. They were characterized using FTIR and single crystal x-ray diffraction. The volatility of these compounds at elevated temperatures was then analyzed, and discussed. The synthesis procedure developed here presents a facile platform for further Np organometallic studies.},
doi = {10.1021/acs.inorgchem.7b02290},
journal = {Inorganic Chemistry},
number = 21,
volume = 56,
place = {United States},
year = {Tue Oct 17 00:00:00 EDT 2017},
month = {Tue Oct 17 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.7b02290
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Cited by: 4 works
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Figures / Tables:

Figure 1 Figure 1: Chemical structures of (A) 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione (FOD), (B) 1,1,1,2,2-pentafluoro-6,6-dimethylheptane3,5-dione (PDHD), (C) 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione (TDHD), and (D) 2,2,6,6-tetramethyl-3,5-heptanedione (TMHD).
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    Figure 6 (p. 8)figure
    Table 2 (p. 8)table
    Figure 10 (p. 9)figure
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