Exploring crown-ether functionalization on the stabilization of hexavalent neptunium

Pyrch, Mikaela M.; Williams, James M.; Forbes, Tori Z.

doi:10.1039/c9cc04393d

Title: Exploring crown-ether functionalization on the stabilization of hexavalent neptunium

Abstract

Crown-ether molecules are used in radiochemical separations due to their high selectivity for a range of metal cations. Previous investigations regarding the interactions of 18-crown-6 (18C6) with ²³⁷Np suggested the formation of a Np(V) inclusion complex, but also reported rapid reduction of Np(VI) to Np(V) in the presence of the ether molecule. Herein, we investigate the impact of crown ether functionalization by exploring the Np(V) and Np(VI) dicyclohexano-18-crown-6 (DCH-18C6) systems. Two [X(DCH-18C6)]₂[Np(VI)O₂Cl₄] compounds (X = K (1) and Na (2)) were crystallized and characterized by single crystal X-ray diffraction and Raman spectroscopy. Additional studies of Np(VI), Np(V), and Np(V)/Np(VI) in solution indicated redox stability in the presence of functionalized crowns and preferential crystallization of Np(VI) DCH-18C6 solids. Furthermore, these results indicate that functionalization of the crown can lead to higher resistance to radiolysis and increased stability of the Np(VI) oxidation state in solution.

Authors:

Pyrch, Mikaela M. ^[1]; Williams, James M. ^[1];

^[1]

University of Iowa, Iowa City, IA (United States)

Publication Date:: Thu Jul 11 00:00:00 EDT 2019

Research Org.:: Univ. of Iowa, Iowa City, IA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1668731

Alternate Identifier(s):: OSTI ID: 1543020

Grant/Contract Number:: SC0013980

Resource Type:: Accepted Manuscript

Journal Name:: ChemComm

Additional Journal Information:: Journal Volume: 55; Journal Issue: 63; Journal ID: ISSN 1359-7345

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Neptunium; crown ether; functionalization; redox stabilization

Citation Formats


                    Pyrch, Mikaela M., Williams, James M., and Forbes, Tori Z. Exploring crown-ether functionalization on the stabilization of hexavalent neptunium.  United States: N. p., 2019. 
Web.  doi:10.1039/c9cc04393d.

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                    Pyrch, Mikaela M., Williams, James M., & Forbes, Tori Z. Exploring crown-ether functionalization on the stabilization of hexavalent neptunium.  United States.  https://doi.org/10.1039/c9cc04393d

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                    Pyrch, Mikaela M., Williams, James M., and Forbes, Tori Z. Thu .  
"Exploring crown-ether functionalization on the stabilization of hexavalent neptunium".  United States.  https://doi.org/10.1039/c9cc04393d.  https://www.osti.gov/servlets/purl/1668731.

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@article{osti_1668731,

  title        = {Exploring crown-ether functionalization on the stabilization of hexavalent neptunium},

  author       = {Pyrch, Mikaela M. and Williams, James M. and Forbes, Tori Z.},

  abstractNote = {Crown-ether molecules are used in radiochemical separations due to their high selectivity for a range of metal cations. Previous investigations regarding the interactions of 18-crown-6 (18C6) with 237Np suggested the formation of a Np(V) inclusion complex, but also reported rapid reduction of Np(VI) to Np(V) in the presence of the ether molecule. Herein, we investigate the impact of crown ether functionalization by exploring the Np(V) and Np(VI) dicyclohexano-18-crown-6 (DCH-18C6) systems. Two [X(DCH-18C6)]2[Np(VI)O2Cl4] compounds (X = K (1) and Na (2)) were crystallized and characterized by single crystal X-ray diffraction and Raman spectroscopy. Additional studies of Np(VI), Np(V), and Np(V)/Np(VI) in solution indicated redox stability in the presence of functionalized crowns and preferential crystallization of Np(VI) DCH-18C6 solids. Furthermore, these results indicate that functionalization of the crown can lead to higher resistance to radiolysis and increased stability of the Np(VI) oxidation state in solution.},

  doi          = {10.1039/c9cc04393d},

  journal      = {ChemComm},

  number       = 63,

  volume       = 55,

  place        = {United States},

  year         = {Thu Jul 11 00:00:00 EDT 2019},

  month        = {Thu Jul 11 00:00:00 EDT 2019}

}

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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
journal, January 2020

Pyrch, Mikaela M.; Bjorklund, Jennifer L.; Williams, James M.
Dalton Transactions, Vol. 49, Issue 20
DOI: 10.1039/d0dt00848f

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Title: Exploring crown-ether functionalization on the stabilization of hexavalent neptunium

Abstract

Citation Formats

Crown ethers in radiochemistry. Advances and prospects journal, September 2000

Extraction of strontium using an irradiated extraction agent of crown structure journal, October 1989

Solvent extraction separation of cesium with dibenzo-24-crown-8 from picrate solution journal, December 1991

Extraction of Uranium(VI) and Plutonium(IV) into Toluene by Crown Ethers from Nitric Acid Solution journal, January 1991

Some studies on the extraction of actinides with crown-ethers journal, January 1987

U6+ Minerals and Inorganic Compounds: Insights into an Expanded Structural Hierarchy of Crystal Structures journal, December 2005

Synthesis and Utilization of New Extractants for Nuclear Hydrometallurgy journal, April 1995

Macrocycle complexation chemistry. 33. Preparation of [Ca(12-crown-4)2][UO2Cl4] and [Ca(OH2)3(15-crown-5)] [UO2Cl4]. Structure of [Ca(OH2)3(15-crown-5)][UO2Cl4] journal, December 1990

Synthesis and structural elucidation of novel uranyl-crown ether compounds isolated from nitric, hydrochloric, sulfuric, and acetic acids journal, June 1991

Synthesis and crystal structure of [UO2(NO3)2(OH2 2]�2(benzo-15-crown-5) journal, June 1992

Synthesis and Structure of the First Transuranium Crown Ether Inclusion Complex: [NpO2([18]Crown-6)]ClO4 journal, February 1998

Crown Ether Inclusion Complexes of the Early Actinide Elements, [AnO 2 (18-crown-6)] n + , An = U, Np, Pu and n = 1, 2: A Relativistic Density Functional Study journal, March 2008

Impacts of Oxo Interactions on Np(V) Crown Ether Complexes journal, May 2018

The complex reaction kinetics of neptunium including redox and extraction process in 30% TBP—nitric acid system journal, March 2017

The effects of radiation chemistry on radiochemistry: when unpaired electrons defy great expectations journal, February 2018

The unusual stability of [NpO2Cl4]2−: Synthesis and characterisation of [NpO2(DPPMO2)2Cl]2[NpO2Cl4] and [Ph3PNH2]2[NpO2Cl4] journal, June 2010

Synthesis, Structure, and Vibrational Properties of [Ph 4 P] 2 NpO 2 Cl 4 and [Ph 4 P] 2 PuO 2 Cl 4 Complexes journal, March 2018

Raman spectra and conformations of dibenzo- and dicyclohexano-18-crown-6 journal, June 1990

Actinyl-cation interactions: experimental and theoretical assessment of [Np( vi )O 2 Cl 4 ] 2− and [U( vi )O 2 Cl 4 ] 2− systems journal, January 2019

Raman spectrometric studies of "cation-cation" complexes of pentavalent actinides in aqueous perchlorate solutions journal, March 1982

The redox chemistry of neptunium in γ-irradiated aqueous nitric acid in the presence of an organic phase journal, October 2015

Radiation chemistry of aqueous solutions of actinides journal, September 1997

On the radiation resistance of crown ethers journal, June 1987

Radiation stability of cis-isomers of dicyclohexano-18-crown-6 journal, October 1996

Impacts of hydrogen bonding interactions with Np( v / vi )O 2 Cl 4 complexes: vibrational spectroscopy, redox behavior, and computational analysis journal, January 2020

Crown ethers in radiochemistry. Advances and prospects
journal, September 2000

Extraction of strontium using an irradiated extraction agent of crown structure
journal, October 1989

Solvent extraction separation of cesium with dibenzo-24-crown-8 from picrate solution
journal, December 1991

Extraction of Uranium(VI) and Plutonium(IV) into Toluene by Crown Ethers from Nitric Acid Solution
journal, January 1991

Some studies on the extraction of actinides with crown-ethers
journal, January 1987

U6+ Minerals and Inorganic Compounds: Insights into an Expanded Structural Hierarchy of Crystal Structures
journal, December 2005

Synthesis and Utilization of New Extractants for Nuclear Hydrometallurgy
journal, April 1995

Macrocycle complexation chemistry. 33. Preparation of [Ca(12-crown-4)2][UO2Cl4] and [Ca(OH2)3(15-crown-5)] [UO2Cl4]. Structure of [Ca(OH2)3(15-crown-5)][UO2Cl4]
journal, December 1990

Synthesis and structural elucidation of novel uranyl-crown ether compounds isolated from nitric, hydrochloric, sulfuric, and acetic acids
journal, June 1991

Synthesis and crystal structure of [UO2(NO3)2(OH2 2]�2(benzo-15-crown-5)
journal, June 1992

Synthesis and Structure of the First Transuranium Crown Ether Inclusion Complex: [NpO2([18]Crown-6)]ClO4
journal, February 1998

Crown Ether Inclusion Complexes of the Early Actinide Elements, [AnO ₂ (18-crown-6)] ^{n +} , An = U, Np, Pu and n = 1, 2: A Relativistic Density Functional Study
journal, March 2008

Impacts of Oxo Interactions on Np(V) Crown Ether Complexes
journal, May 2018

The complex reaction kinetics of neptunium including redox and extraction process in 30% TBP—nitric acid system
journal, March 2017

The effects of radiation chemistry on radiochemistry: when unpaired electrons defy great expectations
journal, February 2018

The unusual stability of [NpO2Cl4]2−: Synthesis and characterisation of [NpO2(DPPMO2)2Cl]2[NpO2Cl4] and [Ph3PNH2]2[NpO2Cl4]
journal, June 2010

Synthesis, Structure, and Vibrational Properties of [Ph ₄ P] ₂ NpO ₂ Cl ₄ and [Ph ₄ P] ₂ PuO ₂ Cl ₄ Complexes
journal, March 2018

Raman spectra and conformations of dibenzo- and dicyclohexano-18-crown-6
journal, June 1990

Actinyl-cation interactions: experimental and theoretical assessment of [Np( vi )O ₂ Cl ₄ ] ²⁻ and [U( vi )O ₂ Cl ₄ ] ²⁻ systems
journal, January 2019

Raman spectrometric studies of "cation-cation" complexes of pentavalent actinides in aqueous perchlorate solutions
journal, March 1982

The redox chemistry of neptunium in γ-irradiated aqueous nitric acid in the presence of an organic phase
journal, October 2015

Radiation chemistry of aqueous solutions of actinides
journal, September 1997

On the radiation resistance of crown ethers
journal, June 1987

Radiation stability of cis-isomers of dicyclohexano-18-crown-6
journal, October 1996

Impacts of hydrogen bonding interactions with Np( v / vi )O ₂ Cl ₄ complexes: vibrational spectroscopy, redox behavior, and computational analysis
journal, January 2020