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Title: Neptunium and plutonium complexes with a sterically encumbered triamidoamine (TREN) scaffold

Abstract

Here, the syntheses and characterization of isostructural neptunium(IV) and plutonium(IV) complexes [MIV(TRENTIPS)(Cl)] [An = Np, Pu; TRENTIPS = {N(CH2CH2NSiPri3)3}3] are reported, along with the demonstration that they are likely reduced to the corresponding neptunium(III) and plutonium(III) products [MIII(TRENTIPS)]; this chemistry provides new platforms from which to target a plethora of unprecedented molecular functionalities in transuranic chemistry and the neptunium(IV) molecule is the first structurally characterized neptunium(IV)–amide complex.

Authors:
 [1];  [1];  [2];  [2];  [1];  [1];  [2]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. The Univ. of Manchester, Manchester (United Kingdom)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1304834
Report Number(s):
LA-UR-16-21047
Journal ID: ISSN 1359-7345; CHCOFS
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
ChemComm
Additional Journal Information:
Journal Volume: 52; Journal Issue: 31; 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

Citation Formats

Brown, Jessie L., Gaunt, Andrew J., King, David M., Liddle, Stephen T., Reilly, Sean D., Scott, Brian L., and Wooles, Ashley J. Neptunium and plutonium complexes with a sterically encumbered triamidoamine (TREN) scaffold. United States: N. p., 2016. Web. doi:10.1039/C6CC01656A.
Brown, Jessie L., Gaunt, Andrew J., King, David M., Liddle, Stephen T., Reilly, Sean D., Scott, Brian L., & Wooles, Ashley J. Neptunium and plutonium complexes with a sterically encumbered triamidoamine (TREN) scaffold. United States. doi:10.1039/C6CC01656A.
Brown, Jessie L., Gaunt, Andrew J., King, David M., Liddle, Stephen T., Reilly, Sean D., Scott, Brian L., and Wooles, Ashley J. Fri . "Neptunium and plutonium complexes with a sterically encumbered triamidoamine (TREN) scaffold". United States. doi:10.1039/C6CC01656A. https://www.osti.gov/servlets/purl/1304834.
@article{osti_1304834,
title = {Neptunium and plutonium complexes with a sterically encumbered triamidoamine (TREN) scaffold},
author = {Brown, Jessie L. and Gaunt, Andrew J. and King, David M. and Liddle, Stephen T. and Reilly, Sean D. and Scott, Brian L. and Wooles, Ashley J.},
abstractNote = {Here, the syntheses and characterization of isostructural neptunium(IV) and plutonium(IV) complexes [MIV(TRENTIPS)(Cl)] [An = Np, Pu; TRENTIPS = {N(CH2CH2NSiPri3)3}3] are reported, along with the demonstration that they are likely reduced to the corresponding neptunium(III) and plutonium(III) products [MIII(TRENTIPS)]; this chemistry provides new platforms from which to target a plethora of unprecedented molecular functionalities in transuranic chemistry and the neptunium(IV) molecule is the first structurally characterized neptunium(IV)–amide complex.},
doi = {10.1039/C6CC01656A},
journal = {ChemComm},
number = 31,
volume = 52,
place = {United States},
year = {2016},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 8 works
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Recent developments in nonaqueous plutonium coordination chemistry
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A Linear trans -Bis(imido) Neptunium(V) Actinyl Analog: Np V (NDipp) 2 ( t Bu 2 bipy) 2 Cl (Dipp = 2,6- i Pr 2 C 6 H 3 )
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Single-Molecule Magnetism in a Single-Ion Triamidoamine Uranium(V) Terminal Mono-Oxo Complex
journal, April 2013

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  • Angewandte Chemie, Vol. 125, Issue 18
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Triamidoamine-Uranium(IV)-Stabilized Terminal Parent Phosphide and Phosphinidene Complexes
journal, March 2014

  • Gardner, Benedict M.; Balázs, Gábor; Scheer, Manfred
  • Angewandte Chemie, Vol. 126, Issue 17
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An Inverted-Sandwich Diuranium μ-η 55 -Cyclo-P 5 Complex Supported by U-P 5 δ-Bonding
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    Works referencing / citing this record:

    Single-Molecule Magnetism in a Single-Ion Triamidoamine Uranium(V) Terminal Mono-Oxo Complex
    journal, April 2013

    • King, David M.; Tuna, Floriana; McMaster, Jonathan
    • Angewandte Chemie International Edition, Vol. 52, Issue 18
    • DOI: 10.1002/anie.201301007

    Triamidoamine-Uranium(IV)-Stabilized Terminal Parent Phosphide and Phosphinidene Complexes
    journal, March 2014

    • Gardner, Benedict M.; Balázs, Gábor; Scheer, Manfred
    • Angewandte Chemie International Edition, Vol. 53, Issue 17
    • DOI: 10.1002/anie.201400798

    Two-Electron Reductive Carbonylation of Terminal Uranium(V) and Uranium(VI) Nitrides to Cyanate by Carbon Monoxide
    journal, July 2014

    • Cleaves, Peter A.; King, David M.; Kefalidis, Christos E.
    • Angewandte Chemie International Edition, Vol. 53, Issue 39
    • DOI: 10.1002/anie.201406203

    The Renaissance of Non-Aqueous Uranium Chemistry
    journal, June 2015


    An Inverted-Sandwich Diuranium μ-η 55 -Cyclo-P 5 Complex Supported by U-P 5 δ-Bonding
    journal, April 2015

    • Gardner, Benedict M.; Tuna, Floriana; McInnes, Eric J. L.
    • Angewandte Chemie International Edition, Vol. 54, Issue 24
    • DOI: 10.1002/anie.201501728

    Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex
    journal, October 2015

    • Gardner, Benedict M.; Balázs, Gábor; Scheer, Manfred
    • Angewandte Chemie International Edition, Vol. 54, Issue 50
    • DOI: 10.1002/anie.201508600

    Recent developments in nonaqueous plutonium coordination chemistry
    journal, June 2010


    Experimental and Theoretical Comparison of Actinide and Lanthanide Bonding in M[N(EPR 2 ) 2 ] 3 Complexes (M = U, Pu, La, Ce; E = S, Se, Te; R = Ph, i Pr, H)
    journal, January 2008

    • Gaunt, Andrew J.; Reilly, Sean D.; Enriquez, Alejandro E.
    • Inorganic Chemistry, Vol. 47, Issue 1
    • DOI: 10.1021/ic701618a

    Low-Valent Molecular Plutonium Halide Complexes
    journal, September 2008

    • Gaunt, Andrew J.; Reilly, Sean D.; Enriquez, Alejandro E.
    • Inorganic Chemistry, Vol. 47, Issue 18
    • DOI: 10.1021/ic8009139

    A Complete Family of Terminal Uranium Chalcogenides, [U(E)(N{SiMe 3 } 2 ) 3 ] (E = O, S, Se, Te)
    journal, September 2012

    • Brown, Jessie L.; Fortier, Skye; Lewis, Richard A.
    • Journal of the American Chemical Society, Vol. 134, Issue 37
    • DOI: 10.1021/ja305712m

    Synthesis and Spectroscopic and Computational Characterization of the Chalcogenido-Substituted Analogues of the Uranyl Ion, [OUE] 2+ (E = S, Se)
    journal, March 2013

    • Brown, Jessie L.; Fortier, Skye; Wu, Guang
    • Journal of the American Chemical Society, Vol. 135, Issue 14
    • DOI: 10.1021/ja402068j

    Synthesis of Uranium–Ligand Multiple Bonds by Cleavage of a Trityl Protecting Group
    journal, December 2013

    • Smiles, Danil E.; Wu, Guang; Hayton, Trevor W.
    • Journal of the American Chemical Society, Vol. 136, Issue 1
    • DOI: 10.1021/ja411423a

    Synthesis and Characterization of an f-Block Terminal Parent Imido [U═NH] Complex: A Masked Uranium(IV) Nitride
    journal, April 2014

    • King, David M.; McMaster, Jonathan; Tuna, Floriana
    • Journal of the American Chemical Society, Vol. 136, Issue 15
    • DOI: 10.1021/ja502405e

    A Linear trans -Bis(imido) Neptunium(V) Actinyl Analog: Np V (NDipp) 2 ( t Bu 2 bipy) 2 Cl (Dipp = 2,6- i Pr 2 C 6 H 3 )
    journal, July 2015

    • Brown, Jessie L.; Batista, Enrique R.; Boncella, James M.
    • Journal of the American Chemical Society, Vol. 137, Issue 30
    • DOI: 10.1021/jacs.5b06667

    Isolation and characterization of a uranium(VI)–nitride triple bond
    journal, May 2013

    • King, David M.; Tuna, Floriana; McInnes, Eric J. L.
    • Nature Chemistry, Vol. 5, Issue 6
    • DOI: 10.1038/nchem.1642

    Harnessing redox activity for the formation of uranium tris(imido) compounds
    journal, July 2014

    • Anderson, Nickolas H.; Odoh, Samuel O.; Yao, Yiyi
    • Nature Chemistry, Vol. 6, Issue 10
    • DOI: 10.1038/nchem.2009

    Triamidoamine uranium(IV)–arsenic complexes containing one-, two- and threefold U–As bonding interactions
    journal, June 2015

    • Gardner, Benedict M.; Balázs, Gábor; Scheer, Manfred
    • Nature Chemistry, Vol. 7, Issue 7
    • DOI: 10.1038/nchem.2279

    Triamidoamine thorium-arsenic complexes with parent arsenide, arsinidiide and arsenido structural motifs
    journal, March 2017

    • Wildman, Elizabeth P.; Balázs, Gábor; Wooles, Ashley J.
    • Nature Communications, Vol. 8, Issue 1
    • DOI: 10.1038/ncomms14769

    Differences in actinide metal–ligand orbital interactions: comparison of U(iv) and Pu(iv) β-ketoiminate N,O donor complexes
    journal, January 2011

    • Schnaars, David D.; Batista, Enrique R.; Gaunt, Andrew J.
    • Chemical Communications, Vol. 47, Issue 27
    • DOI: 10.1039/c1cc12409a

    Uncovering f-element bonding differences and electronic structure in a series of 1 : 3 and 1 : 4 complexes with a diselenophosphinate ligand
    journal, January 2013

    • Jones, Matthew B.; Gaunt, Andrew J.; Gordon, John C.
    • Chemical Science, Vol. 4, Issue 3
    • DOI: 10.1039/c2sc21806b

    Recent developments in actinide–ligand multiple bonding
    journal, January 2013


    Formate complexes of titanium( iv ) supported by a triamido-amine ligand
    journal, January 2018

    • Paparo, A.; van Krüchten, F. D.; Spaniol, T. P.
    • Dalton Transactions, Vol. 47, Issue 10
    • DOI: 10.1039/c7dt04859a

    A neptunium( v )-mediated interwoven transuranium-rotaxane network incorporating a mechanically interlocked [ c 2]daisy chain unit
    journal, January 2018

    • Mei, Lei; Xu, Chao; Wu, Qun-yan
    • Chemical Communications, Vol. 54, Issue 62
    • DOI: 10.1039/c8cc05122d

    Homologation and functionalization of carbon monoxide by a recyclable uranium complex
    journal, May 2012

    • Gardner, B. M.; Stewart, J. C.; Davis, A. L.
    • Proceedings of the National Academy of Sciences, Vol. 109, Issue 24
    • DOI: 10.1073/pnas.1203417109

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


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


    Triamidoamine thorium-arsenic complexes with parent arsenide, arsinidiide and arsenido structural motifs
    journal, March 2017

    • Wildman, Elizabeth P.; Balázs, Gábor; Wooles, Ashley J.
    • Nature Communications, Vol. 8, Issue 1
    • DOI: 10.1038/ncomms14769

    Formate complexes of titanium( iv ) supported by a triamido-amine ligand
    journal, January 2018

    • Paparo, A.; van Krüchten, F. D.; Spaniol, T. P.
    • Dalton Transactions, Vol. 47, Issue 10
    • DOI: 10.1039/c7dt04859a

    A neptunium( v )-mediated interwoven transuranium-rotaxane network incorporating a mechanically interlocked [ c 2]daisy chain unit
    journal, January 2018

    • Mei, Lei; Xu, Chao; Wu, Qun-yan
    • Chemical Communications, Vol. 54, Issue 62
    • DOI: 10.1039/c8cc05122d