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

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.

doi:10.1021/acs.inorgchem.7b02290

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:

^[1]; Parker, T. Gannon ^[2]; Dickens, Sara M. ^[2];

^[1]; Oliver, Allen G. ^[3]; Wall, Donald ^[2]; Wall, Nathalie A. ^[2];

^[1];

^[1]

Idaho National Lab. (INL), Idaho Falls, ID (United States)
Washington State Univ., Pullman, WA (United States)
Univ. of Notre Dame, Notre Dame, IN (United States)

Publication Date:: 2017-10-17

Research Org.:: Idaho National Lab. (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         = {2017},

  month        = {10}

}

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https://doi.org/10.1021/acs.inorgchem.7b02290

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Cited by: 4 works

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Figures / Tables:

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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Works referenced in this record:

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Jiang, Yinzhu; Liu, Mingfei; Wang, Yanyan
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Abdunnabi, H. M.; Ananyev, A. V.
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The Preparation of Solid Neptunium Compounds ¹
journal, November 1948

Fried, Sherman; Davidson, Norman
Journal of the American Chemical Society, Vol. 70, Issue 11
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Reduction behavior of neptunium(V) at a gold or platinum electrode during controlled potential electrolysis and procedures for electrochemical preparations of neptunium(IV) and (III)
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Kitatsuji, Yoshihiro; Kimura, Takaumi; Kihara, Sorin
Journal of Electroanalytical Chemistry, Vol. 641, Issue 1-2
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Separation and preconcentration of actinides by extraction chromatography using a supported liquid anion exchanger: application to the characterization of high-level nuclear waste solutions
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Works referencing / citing this record:

Structure and properties of [(4,6- ^t Bu ₂ C ₆ H ₂ O) ₂ Se] ₂ An(THF) ₂ , An = U, Np, and their reaction with p -benzoquinone
journal, January 2018

Myers, Alexander J.; Rungthanaphatsophon, Pokpong; Behrle, Andrew C.
Chemical Communications, Vol. 54, Issue 74
DOI: 10.1039/c8cc05244a

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

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Production of certified reference materials in support of domestic nuclear forensics programs require volatile precursors for introduction into electromagnetic isotopic separation instruments. β-diketone chelates of tetravalent actinides are known for their high volatility, but previously developed synthetic approaches require starting material (NpCl₄) that is prohibitively difficult and hazardous to prepare. An alternative strategy was developed here that uses controlled potential electrolysis to reduce neptunium to the tetravalent state in submolar concentrations of hydrochloric acid. Four different β-diketone ligands of varying degrees of fluorination were reacted with an aqueous solution of Np⁴⁺. Products of this reaction were characterized via X-ray diffractionmore »« less
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Using the flow method the authors have determined the temperature dependence of the saturated vapor pressure of a series of ..beta..-diketonates of neptunium(VI) and -(IV). In studying the complexes Np(PTFA)/sub 4/ (PTFA = pivaloyltrifluoroacetonate), Np(HFA)/sub 4/ (HFA = hexafluoroacetylacetonate) and Np(HFA)/sub 4/ x TMPO (TMPO = trimethylphosphinoxide), the authors observed that the chelate Np(HFA)/sub 4/, being the most volatile of the listed compounds, at the same time displays insufficient stability; determination of the vapor pressure for this compound was carried out with saturation of the carrier gas with vapors of free H-HFA. It has been established that among the ..beta..-diketonatesmore »« less
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The authors have recently described the synthesis of volatile pivaloyltrifluoroacetonate derivatives of neptunium (neptunyl), NpO/sub 2/(PTFA)/sub 2/, based on adducts with neutral ligands of varying ligand strengths. Not all of the adducts were stable with respect to decomposition to give Np (PTFA)/sub 4/ during sublimation. Since the degree of decomposition was found to depend on the basicity of the neutral ligand, it would also be expected to depend on the basicity of the ..beta..-diketonate anion. Their main goal in the present paper was to investigate the range of ..beta..-diketonate and neutral ligands which are capable of forming volatile, yet thermallymore »« less
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In this review, volatile coordination and organic compounds of neptunium and plutonium are described, including complex halides, alkoxides, borohydrides, ..beta..-diketonates, phthalocyanines, and organometallic ..pi..-complexes. Comparison is made with analogous compounds of other f-elements (particularly, uranium and thorium). The prospects of practical use of volatile compounds of neptunium and plutonium are discussed.
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Title: Synthesis and Crystal Structures of Volatile Neptunium(IV) β-Diketonates

Abstract

Citation Formats

Figures / Tables:

The state of nuclear forensics journal, January 2013

A brief introduction to analytical methods in nuclear forensics journal, July 2012

Vapour-pressures of NpF6 and PuF6; thermodynamic calculations with UF6, NpF6 and PuF6 journal, September 1959

Volatile Rare Earth Chelates journal, November 1965

Thermogravimetric studies of metal β-diketonates journal, August 1967

Rare earth chelates of 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedione journal, June 1967

Fractional sublimation of the β-diketone chelates of the lanthanide and related elements journal, January 1968

Decomposition Behavior of M(DPM) n (DPM = 2,2,6,6-Tetramethyl-3,5-heptanedionato; n = 2, 3, 4) journal, November 2006

Volatile chelates of quadrivalent actinides journal, July 1970

Volatile β-diketonates of neptunium(IV) and (VI) journal, May 1988

Diethyldithiocarbamates of quadrivalent actinides journal, May 1968

Interaction of tetravalent actinide double chlorides with metallic aluminium journal, November 1990

The Preparation of Solid Neptunium Compounds 1 journal, November 1948

Reduction behavior of neptunium(V) at a gold or platinum electrode during controlled potential electrolysis and procedures for electrochemical preparations of neptunium(IV) and (III) journal, March 2010

Separation and preconcentration of actinides by extraction chromatography using a supported liquid anion exchanger: application to the characterization of high-level nuclear waste solutions journal, June 1995

An empirical correction for absorption anisotropy journal, January 1995

Crystal structure refinement with SHELXL journal, January 2015

Single-crystal structure validation with the program PLATON journal, January 2003

Tricyclopentadienylneptunium-chlorid journal, June 1966

Tetrakis(cyclopentadienyl)neptunium(IV) journal, August 1968

Bis(cyclooctatetraenyl)neptunium(IV) journal, March 1996

Neptunium chloro-complexes journal, January 1966

Structure and properties of [(4,6- t Bu 2 C 6 H 2 O) 2 Se] 2 An(THF) 2 , An = U, Np, and their reaction with p -benzoquinone journal, January 2018

The state of nuclear forensics
journal, January 2013

A brief introduction to analytical methods in nuclear forensics
journal, July 2012

Vapour-pressures of NpF6 and PuF6; thermodynamic calculations with UF6, NpF6 and PuF6
journal, September 1959

Volatile Rare Earth Chelates
journal, November 1965

Thermogravimetric studies of metal β-diketonates
journal, August 1967

Rare earth chelates of 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedione
journal, June 1967

Fractional sublimation of the β-diketone chelates of the lanthanide and related elements
journal, January 1968

Decomposition Behavior of M(DPM) _n (DPM = 2,2,6,6-Tetramethyl-3,5-heptanedionato; n = 2, 3, 4)
journal, November 2006

Volatile chelates of quadrivalent actinides
journal, July 1970

Volatile β-diketonates of neptunium(IV) and (VI)
journal, May 1988

Diethyldithiocarbamates of quadrivalent actinides
journal, May 1968

Interaction of tetravalent actinide double chlorides with metallic aluminium
journal, November 1990

The Preparation of Solid Neptunium Compounds ¹
journal, November 1948

Reduction behavior of neptunium(V) at a gold or platinum electrode during controlled potential electrolysis and procedures for electrochemical preparations of neptunium(IV) and (III)
journal, March 2010

Separation and preconcentration of actinides by extraction chromatography using a supported liquid anion exchanger: application to the characterization of high-level nuclear waste solutions
journal, June 1995

An empirical correction for absorption anisotropy
journal, January 1995

Crystal structure refinement with SHELXL
journal, January 2015

Single-crystal structure validation with the program PLATON
journal, January 2003

Tricyclopentadienylneptunium-chlorid
journal, June 1966

Tetrakis(cyclopentadienyl)neptunium(IV)
journal, August 1968

Bis(cyclooctatetraenyl)neptunium(IV)
journal, March 1996

Neptunium chloro-complexes
journal, January 1966

Structure and properties of [(4,6- ^t Bu ₂ C ₆ H ₂ O) ₂ Se] ₂ An(THF) ₂ , An = U, Np, and their reaction with p -benzoquinone
journal, January 2018