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Title: Structure and properties of [(4,6- tBu 2C 6H 2O) 2Se] 2An(THF) 2, An = U, Np, and their reaction with p-benzoquinone

Abstract

The synthesis and characterization of U(iv) and Np(iv) selenium bis(phenolate) complexes are reported. The reaction of two equivalents of the U(iv) complex with p-benzoquinone results in the formation of a U(v)-U(v) species with a bridging reduced quinone. Here, this represents a rare example of high-valent uranium chemistry as well as a rare example of a neptunium aryloxide complex.

Authors:
 [1];  [2];  [2];  [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2]
  1. Univ. of Missouri, Columbia, MO (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. Univ. of Missouri, Columbia, MO (United States). Dept. of Chemistry
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS) (SC-27); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1476601
Alternate Identifier(s):
OSTI ID: 1467921
Grant/Contract Number:  
AC02-05CH11231; SC0014174; SC0014664
Resource Type:
Accepted Manuscript
Journal Name:
ChemComm
Additional Journal Information:
Journal Volume: 54; Journal Issue: 74; 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

Myers, Alexander J., Rungthanaphatsophon, Pokpong, Behrle, Andrew C., Vilanova, Sean P., Kelley, Stephen P., Lukens, Wayne W., and Walensky, Justin R. Structure and properties of [(4,6-tBu2C6H2O)2Se]2An(THF)2, An = U, Np, and their reaction with p-benzoquinone. United States: N. p., 2018. Web. doi:10.1039/c8cc05244a.
Myers, Alexander J., Rungthanaphatsophon, Pokpong, Behrle, Andrew C., Vilanova, Sean P., Kelley, Stephen P., Lukens, Wayne W., & Walensky, Justin R. Structure and properties of [(4,6-tBu2C6H2O)2Se]2An(THF)2, An = U, Np, and their reaction with p-benzoquinone. United States. doi:10.1039/c8cc05244a.
Myers, Alexander J., Rungthanaphatsophon, Pokpong, Behrle, Andrew C., Vilanova, Sean P., Kelley, Stephen P., Lukens, Wayne W., and Walensky, Justin R. Fri . "Structure and properties of [(4,6-tBu2C6H2O)2Se]2An(THF)2, An = U, Np, and their reaction with p-benzoquinone". United States. doi:10.1039/c8cc05244a. https://www.osti.gov/servlets/purl/1476601.
@article{osti_1476601,
title = {Structure and properties of [(4,6-tBu2C6H2O)2Se]2An(THF)2, An = U, Np, and their reaction with p-benzoquinone},
author = {Myers, Alexander J. and Rungthanaphatsophon, Pokpong and Behrle, Andrew C. and Vilanova, Sean P. and Kelley, Stephen P. and Lukens, Wayne W. and Walensky, Justin R.},
abstractNote = {The synthesis and characterization of U(iv) and Np(iv) selenium bis(phenolate) complexes are reported. The reaction of two equivalents of the U(iv) complex with p-benzoquinone results in the formation of a U(v)-U(v) species with a bridging reduced quinone. Here, this represents a rare example of high-valent uranium chemistry as well as a rare example of a neptunium aryloxide complex.},
doi = {10.1039/c8cc05244a},
journal = {ChemComm},
number = 74,
volume = 54,
place = {United States},
year = {2018},
month = {8}
}

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Cited by: 2 works
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    Works referencing / citing this record:

    CCDC 1851817: Experimental Crystal Structure Determination: FIFYUR : bis(tetrahydrofuran)-bis(2,2'-selanylbis(4,6-di-t-butylphenolato))-uranium(iv) toluene solvate
    dataset, August 2018

    • Myers, Alexander J.; Rungthanaphatsophon, Pokpong; Behrle, Andrew C.
    • Cambridge Structural Database (CSD)
    • DOI: 10.5517/ccdc.csd.cc204z16

    Molecular and Electronic Structures of Eight-Coordinate Uranium Bipyridine Complexes: A Rare Example of a Bipy 2– Ligand Coordinated to a U 4+ Ion
    journal, February 2017


    Cerium(III/IV) Formamidinate Chemistry, and a Stable Cerium(IV) Diolate
    journal, March 2014

    • Werner, Daniel; Deacon, Glen B.; Junk, Peter C.
    • Chemistry - A European Journal, Vol. 20, Issue 15
    • DOI: 10.1002/chem.201304582

    Electron-transfer reactions of trivalent uranium. Preparation and structure of the uranium metallocene compounds (MeC5H4)3U:NPh and [(MeC5H4)3U]2[.mu.-.eta.1,.eta.2-PhNCO]
    journal, January 1985

    • Brennan, John G.; Andersen, Richard A.
    • Journal of the American Chemical Society, Vol. 107, Issue 2
    • DOI: 10.1021/ja00288a047

    Synthesis of Uranium(VI) Terminal Oxo Complexes: Molecular Geometry Driven by the Inverse Trans -Influence
    journal, March 2012

    • Kosog, Boris; La Pierre, Henry S.; Heinemann, Frank W.
    • Journal of the American Chemical Society, Vol. 134, Issue 11
    • DOI: 10.1021/ja211618v

    Additive Covalent Radii for Single-, Double-, and Triple-Bonded Molecules and Tetrahedrally Bonded Crystals: A Summary
    journal, September 2014

    • Pyykkö, Pekka
    • The Journal of Physical Chemistry A, Vol. 119, Issue 11
    • DOI: 10.1021/jp5065819

    Actinide alkoxide chemistry
    journal, September 1990

    • Van der Sluys, W. G.; Sattelberger, A. P.
    • Chemical Reviews, Vol. 90, Issue 6
    • DOI: 10.1021/cr00104a005

    Actinide and rare earth ions in single crystals of ThO2: Preparation, EPR studies and related problems
    journal, August 1986


    Cation-Cation Interactions, Magnetic Communication, and Reactivity of the Pentavalent Uranium Ion [U(N t Bu) 2 ] +
    journal, May 2009

    • Spencer, Liam P.; Schelter, Eric J.; Yang, Ping
    • Angewandte Chemie International Edition, Vol. 48, Issue 21
    • DOI: 10.1002/anie.200806190

    CCDC 1851820: Experimental Crystal Structure Determination
    dataset, August 2018

    • Myers, Alexander J.; Rungthanaphatsophon, Pokpong; Behrle, Andrew C.
    • Cambridge Structural Database (CSD)
    • DOI: 10.5517/ccdc.csd.cc204z49

    Magnetic Properties and Electronic Structure of Neptunyl(VI) Complexes: Wavefunctions, Orbitals, and Crystal-Field Models
    journal, May 2014

    • Gendron, Frédéric; Páez-Hernández, Dayán; Notter, François-Paul
    • Chemistry - A European Journal, Vol. 20, Issue 26
    • DOI: 10.1002/chem.201305039

    Dimeric Rare-Earth BINOLate Complexes: Activation of 1,4-Benzoquinone through Lewis Acid Promoted Potential Shifts
    journal, March 2013

    • Robinson, Jerome R.; Booth, Corwin H.; Carroll, Patrick J.
    • Chemistry - A European Journal, Vol. 19, Issue 19
    • DOI: 10.1002/chem.201300026

    EasySpin, a comprehensive software package for spectral simulation and analysis in EPR
    journal, January 2006


    Uranium Tetrakis-Aryloxide Derivatives Supported by Tetraazacyclododecane: Synthesis of Air-Stable, Coordinatively-Unsaturated U(IV) and U(V) Complexes
    journal, November 2016


    Effects of small distortions on the EPR of the Γ 6 state ( T d symmetry) of Np(BH 3 CH 3 ) 4 diluted in Zr(BH 3 CH 3 ) 4
    journal, June 1984

    • Gamp, E.; Edelstein, N.
    • The Journal of Chemical Physics, Vol. 80, Issue 12
    • DOI: 10.1063/1.446676

    Analysis of the optical spectrum of Np(BD 4 ) 4 diluted in Zr(BD 4 ) 4 and the magnetic properties of Np(BH 4 ) 4 and Np(BH 3 CH 3 ) 4
    journal, June 1984

    • Rajnak, K.; Banks, R. H.; Gamp, E.
    • The Journal of Chemical Physics, Vol. 80, Issue 12
    • DOI: 10.1063/1.446675

    Polynuclear Cation−Cation Complexes of Pentavalent Uranyl: Relating Stability and Magnetic Properties to Structure
    journal, December 2008

    • Nocton, Grégory; Horeglad, Pawel; Pécaut, Jacques
    • Journal of the American Chemical Society, Vol. 130, Issue 49
    • DOI: 10.1021/ja804766r

    Small Molecule Activation by Uranium Tris(aryloxides): Experimental and Computational Studies of Binding of N 2 , Coupling of CO, and Deoxygenation Insertion of CO 2 under Ambient Conditions
    journal, June 2011

    • Mansell, Stephen M.; Kaltsoyannis, Nikolas; Arnold, Polly L.
    • Journal of the American Chemical Society, Vol. 133, Issue 23
    • DOI: 10.1021/ja2019492

    CCDC 1851819: Experimental Crystal Structure Determination: FIFXOK : bis(tetrahydrofuran)-bis(2,2'-selanylbis(4,6-di-t-butylphenolato))-neptunium(iv) toluene solvate
    dataset, June 2018

    • Myers, Alexander J.; Rungthanaphatsophon, Pokpong; Behrle, Andrew C.
    • Cambridge Structural Database (CSD)
    • DOI: 10.5517/ccdc.csd.cc204z38

    Carbon Dioxide Activation by a Uranium(III) Complex Derived from a Chelating Bis(aryloxide) Ligand
    journal, May 2017


    Magnetic Memory Effect in a Transuranic Mononuclear Complex
    journal, January 2011

    • Magnani, Nicola; Apostolidis, Christos; Morgenstern, Alfred
    • Angewandte Chemie International Edition, Vol. 50, Issue 7
    • DOI: 10.1002/anie.201006619

    Uranium Tris-aryloxide Derivatives Supported by Triazacyclononane:  Engendering a Reactive Uranium(III) Center with a Single Pocket for Reactivity
    journal, April 2003

    • Castro-Rodriguez, Ingrid; Olsen, Kristian; Gantzel, Peter
    • Journal of the American Chemical Society, Vol. 125, Issue 15
    • DOI: 10.1021/ja028342n

    Halide Effects in the Synthesis of Mixed Uranium(IV) Aryloxide−Halide Compounds
    journal, August 1998

    • McKee, Steven D.; Burns, Carol J.; Avens, Larry R.
    • Inorganic Chemistry, Vol. 37, Issue 16
    • DOI: 10.1021/ic9803309

    Magnetic properties of a fourfold degenerate state: Np4+ ion diluted in Cs2ZrCl6 crystal
    journal, June 2014

    • Hernández, Dayán Páez; Bolvin, Hélène
    • Journal of Electron Spectroscopy and Related Phenomena, Vol. 194
    • DOI: 10.1016/j.elspec.2014.03.002

    Early actinide alkoxide chemistry. Synthesis, characterization, and molecular structures of thorium(IV) and uranium(IV) aryloxide complexes
    journal, December 1992

    • Berg, John M.; Clark, David L.; Huffman, John C.
    • Journal of the American Chemical Society, Vol. 114, Issue 27
    • DOI: 10.1021/ja00053a017

    Synthesis and Crystal Structures of Volatile Neptunium(IV) β-Diketonates
    journal, October 2017


    Paramagnetic Resonance of Tetravalent Neptunium‐237 in Single Crystals of ThO 2
    journal, January 1972

    • Richardson, Riley P.; Gruber, John B.
    • The Journal of Chemical Physics, Vol. 56, Issue 1
    • DOI: 10.1063/1.1676855

    Some ethoxide compounds of neptunium
    journal, April 1967


    Magnetism and electron spin resonance in single crystalline β-AgNpO2(SeO3)
    journal, November 2004


    Electron paramagnetic resonance and electron nuclear double resonance of 237‐neptunium hexafluoride in uranium hexafluoride single crystals
    journal, March 1981

    • Butler, James E.; Hutchison, Clyde A.
    • The Journal of Chemical Physics, Vol. 74, Issue 6
    • DOI: 10.1063/1.441521