Heptavalent Neptunium in a Gas-Phase Complex: (NpVIIO3+)(NO3–)2

Dau, Phuong D.; Maurice, Remi; Renault, Eric; Gibson, John K.

doi:10.1021/acs.inorgchem.6b01617

Title: Heptavalent Neptunium in a Gas-Phase Complex: (Np^VIIO₃⁺)(NO₃^–)₂

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Abstract

A central goal of chemistry is to achieve ultimate oxidation states, including in gas-phase complexes with no condensed phase perturbations. In the case of the actinide elements, the highest established oxidation states are labile Pu(VII) and somewhat more stable Np(VII). We have synthesized and characterized gas-phase AnO₃(NO₃)₂- complexes for An = U, Np, and Pu by endothermic NO₂ elimination from AnO₂(NO₃)₃-. It was previously demonstrated that the PuO₃+ core of PuO₃(NO₃)₂- has a Pu—O• radical bond such that the oxidation state is Pu(VI); it follows that in UO₃(NO₃)₂- it is the stable U(VI) oxidation state. On the basis of the relatively more facile synthesis of NpO₃(NO₃)₂-, a Np(VII) oxidation state is inferred. This interpretation is substantiated by reactivity of the three complexes: NO₂ spontaneously adds to UO₃(NO₃)₂- and PuO₃(NO₃)₂- but not to NpO₃(NO₃)₂-. This unreactive character is attributed to a Np(VII)O₃+ core with three stable Np=O bonds, this in contrast to reactive U—O• and Pu—O• radical bonds. The computed structures and reaction energies for the three AnO₃(NO₃)₂- support the conclusion that the oxidation states are U(VI), Np(VII), and Pu(VI). These results establish the extreme Np(VII) oxidation state in a gas-phase complex, and demonstrate the inherently greater stability of Np(VII) versusmore » Pu(VII).« less

Authors:

Dau, Phuong D. ^[1]; Maurice, Remi ^[2]; Renault, Eric ^[3]; Gibson, John K. ^[1]

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Laboratory of Subatomic Physics and Associated Technologies (SUBATECH), UMR CNRS 6457, IN2P3/EMN Nantes, Univ. of Nantes (France)
Lab. of Chemical Interdisciplinarity, Synthesis, Analysis and Modeling (CEISAM), UMR CNRS 6230, Univ. of Nantes (France)

Publication Date:: Thu Sep 15 00:00:00 EDT 2016

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Large Intensive Computing Equipment (GENCI); Intensive Calculation Center of Pays de la Loire (CCIPL)

OSTI Identifier:: 1436600

Grant/Contract Number:: AC02-05CH11231; 2015-c2015085117

Resource Type:: Accepted Manuscript

Journal Name:: Inorganic Chemistry

Additional Journal Information:: Journal Volume: 55; Journal Issue: 19; 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

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                    Dau, Phuong D., Maurice, Remi, Renault, Eric, and Gibson, John K. Heptavalent Neptunium in a Gas-Phase Complex: (NpVIIO3+)(NO3–)2.  United States: N. p., 2016. 
Web.  doi:10.1021/acs.inorgchem.6b01617.

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                    Dau, Phuong D., Maurice, Remi, Renault, Eric, & Gibson, John K. Heptavalent Neptunium in a Gas-Phase Complex: (NpVIIO3+)(NO3–)2.  United States.  https://doi.org/10.1021/acs.inorgchem.6b01617

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                    Dau, Phuong D., Maurice, Remi, Renault, Eric, and Gibson, John K. Thu .  
"Heptavalent Neptunium in a Gas-Phase Complex: (NpVIIO3+)(NO3–)2".  United States.  https://doi.org/10.1021/acs.inorgchem.6b01617.  https://www.osti.gov/servlets/purl/1436600.

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@article{osti_1436600,

  title        = {Heptavalent Neptunium in a Gas-Phase Complex: (NpVIIO3+)(NO3–)2},

  author       = {Dau, Phuong D. and Maurice, Remi and Renault, Eric and Gibson, John K.},

  abstractNote = {A central goal of chemistry is to achieve ultimate oxidation states, including in gas-phase complexes with no condensed phase perturbations. In the case of the actinide elements, the highest established oxidation states are labile Pu(VII) and somewhat more stable Np(VII). We have synthesized and characterized gas-phase AnO3(NO3)2- complexes for An = U, Np, and Pu by endothermic NO2 elimination from AnO2(NO3)3-. It was previously demonstrated that the PuO3+ core of PuO3(NO3)2- has a Pu—O• radical bond such that the oxidation state is Pu(VI); it follows that in UO3(NO3)2- it is the stable U(VI) oxidation state. On the basis of the relatively more facile synthesis of NpO3(NO3)2-, a Np(VII) oxidation state is inferred. This interpretation is substantiated by reactivity of the three complexes: NO2 spontaneously adds to UO3(NO3)2- and PuO3(NO3)2- but not to NpO3(NO3)2-. This unreactive character is attributed to a Np(VII)O3+ core with three stable Np=O bonds, this in contrast to reactive U—O• and Pu—O• radical bonds. The computed structures and reaction energies for the three AnO3(NO3)2- support the conclusion that the oxidation states are U(VI), Np(VII), and Pu(VI). These results establish the extreme Np(VII) oxidation state in a gas-phase complex, and demonstrate the inherently greater stability of Np(VII) versus Pu(VII).},

  doi          = {10.1021/acs.inorgchem.6b01617},

  journal      = {Inorganic Chemistry},

  number       = 19,

  volume       = 55,

  place        = {United States},

  year         = {Thu Sep 15 00:00:00 EDT 2016},

  month        = {Thu Sep 15 00:00:00 EDT 2016}

}

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Title: Heptavalent Neptunium in a Gas-Phase Complex: (NpVIIO3+)(NO3–)2

Abstract

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Title: Heptavalent Neptunium in a Gas-Phase Complex: (Np^VIIO₃⁺)(NO₃^–)₂