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Title: Protactinium and the intersection of actinide and transition metal chemistry

Abstract

The role of the 5f and 6d orbitals in the chemistry of the actinide elements has been of considerable interest since their discovery and synthesis. Relativistic effects cause the energetics of the 5f and 6d orbitals to change as the actinide series is traversed left to right imparting a rich and complex chemistry. The 5f and 6d atomic states cross in energy at protactinium (Pa), making it a potential intersection between transition metal and actinide chemistries. Herein, we report the synthesis of a Pa-peroxo cluster, A 6Pa 4O(O 2) 6F 12 [A = Rb, Cs, (CH 3) 4N], formed in pursuit of an actinide polyoxometalate. Quantum chemical calculations at the density functional theory level demonstrate equal 5f and 6d orbital participation in the chemistry of Pa and increasing 5f orbital participation for the heavier actinides. Periodic changes in orbital character to the bonding in the early actinides highlights the influence of the 5f orbitals in their reactivity and chemical structure.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  2. Univ. de Lille, Lille (France). Physique des Lasers Atomes et Molecules
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1426227
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wilson, Richard E., De Sio, Stephanie, and Vallet, Valerie. Protactinium and the intersection of actinide and transition metal chemistry. United States: N. p., 2018. Web. doi:10.1038/s41467-018-02972-z.
Wilson, Richard E., De Sio, Stephanie, & Vallet, Valerie. Protactinium and the intersection of actinide and transition metal chemistry. United States. doi:10.1038/s41467-018-02972-z.
Wilson, Richard E., De Sio, Stephanie, and Vallet, Valerie. Mon . "Protactinium and the intersection of actinide and transition metal chemistry". United States. doi:10.1038/s41467-018-02972-z. https://www.osti.gov/servlets/purl/1426227.
@article{osti_1426227,
title = {Protactinium and the intersection of actinide and transition metal chemistry},
author = {Wilson, Richard E. and De Sio, Stephanie and Vallet, Valerie},
abstractNote = {The role of the 5f and 6d orbitals in the chemistry of the actinide elements has been of considerable interest since their discovery and synthesis. Relativistic effects cause the energetics of the 5f and 6d orbitals to change as the actinide series is traversed left to right imparting a rich and complex chemistry. The 5f and 6d atomic states cross in energy at protactinium (Pa), making it a potential intersection between transition metal and actinide chemistries. Herein, we report the synthesis of a Pa-peroxo cluster, A6Pa4O(O2)6F12 [A = Rb, Cs, (CH3)4N], formed in pursuit of an actinide polyoxometalate. Quantum chemical calculations at the density functional theory level demonstrate equal 5f and 6d orbital participation in the chemistry of Pa and increasing 5f orbital participation for the heavier actinides. Periodic changes in orbital character to the bonding in the early actinides highlights the influence of the 5f orbitals in their reactivity and chemical structure.},
doi = {10.1038/s41467-018-02972-z},
journal = {Nature Communications},
issn = {2041-1723},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {2}
}

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Free Publicly Available Full Text
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Cited by: 6 works
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    journal, May 2014

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    • Angewandte Chemie International Edition, Vol. 53, Issue 28
    • DOI: 10.1002/anie.201402050

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    journal, June 2015


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    • DOI: 10.1002/chem.201404551

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    • DOI: 10.1038/nchem.2009

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    Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
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    Covalency in the uranyl ion: A polarized x-ray spectroscopic study
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    • Denning, R. G.; Green, J. C.; Hutchings, T. E.
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    • DOI: 10.1063/1.1856451

    Energy-consistent relativistic pseudopotentials and correlation consistent basis sets for the 4d elements Y–Pd
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    • Peterson, Kirk A.; Figgen, Detlev; Dolg, Michael
    • The Journal of Chemical Physics, Vol. 126, Issue 12
    • DOI: 10.1063/1.2647019

    Energy-consistent pseudopotentials and correlation consistent basis sets for the 5d elements Hf–Pt
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    • Figgen, Detlev; Peterson, Kirk A.; Dolg, Michael
    • The Journal of Chemical Physics, Vol. 130, Issue 16
    • DOI: 10.1063/1.3119665

    Effect of spin-orbit coupling on the actinide dioxides AnO 2 (An=Th, Pa, U, Np, Pu, and Am): A screened hybrid density functional study
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    • Wen, Xiao-Dong; Martin, Richard L.; Roy, Lindsay E.
    • The Journal of Chemical Physics, Vol. 137, Issue 15
    • DOI: 10.1063/1.4757615

    Toward reliable density functional methods without adjustable parameters: The PBE0 model
    journal, April 1999

    • Adamo, Carlo; Barone, Vincenzo
    • The Journal of Chemical Physics, Vol. 110, Issue 13
    • DOI: 10.1063/1.478522

    Towards a first principles prediction of p K a : COSMO-RS and the cluster-continuum approach
    journal, February 2010


    Synthesis of Imido Analogs of the Uranyl Ion
    journal, December 2005


    Synthesis and Structure of a Terminal Uranium Nitride Complex
    journal, June 2012