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Title: [Am(C 5Me 4H) 3], an organometallic americium complex

Abstract

Organometallic synthetic chemistry of transplutonium elements is an area that has been stagnant for decades. Here, we observe the small-scale synthesis, isolated yield, single-crystal X-ray structure, 1H NMR, solution/solid-state UV-vis-nIR spectroscopy, and Density Functional Theory/ab initio Wave Functional Theory calculations on an Am3+ organometallic complex,[Am(C 5Me 4H) 3]. This constitutes the first quantitative data on Am–C bonding in a molecular species.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [1];  [1];  [3];  [4];  [5];  [1];  [1];  [4];  [1];  [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Florida State Univ., Tallahassee, FL (United States)
  3. Univ. of Iowa, Iowa City, IA (United States)
  4. Philipps-Universität Marburg (Germany)
  5. Univ. of California, Irvine, CA (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1542857
Alternate Identifier(s):
OSTI ID: 1545167
Report Number(s):
LA-UR-19-25159
Journal ID: ISSN 1433-7851
Grant/Contract Number:  
89233218CNA000001
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 58; Journal Issue: 34; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Goodwin, Conrad, Su, Jing, Albrecht-Schmitt, Thomas, Blake, Anastasia, Batista, Enrique, Daly, Scott, Dehnen, Stefanie, Evans, William, Gaunt, Andrew, Kozimor, Stosh, Lichtenberger, Niels, Scott, Brian, and Yang, Ping. [Am(C5Me4H)3], an organometallic americium complex. United States: N. p., 2019. Web. doi:10.1002/anie.201905225.
Goodwin, Conrad, Su, Jing, Albrecht-Schmitt, Thomas, Blake, Anastasia, Batista, Enrique, Daly, Scott, Dehnen, Stefanie, Evans, William, Gaunt, Andrew, Kozimor, Stosh, Lichtenberger, Niels, Scott, Brian, & Yang, Ping. [Am(C5Me4H)3], an organometallic americium complex. United States. doi:10.1002/anie.201905225.
Goodwin, Conrad, Su, Jing, Albrecht-Schmitt, Thomas, Blake, Anastasia, Batista, Enrique, Daly, Scott, Dehnen, Stefanie, Evans, William, Gaunt, Andrew, Kozimor, Stosh, Lichtenberger, Niels, Scott, Brian, and Yang, Ping. Wed . "[Am(C5Me4H)3], an organometallic americium complex". United States. doi:10.1002/anie.201905225.
@article{osti_1542857,
title = {[Am(C5Me4H)3], an organometallic americium complex},
author = {Goodwin, Conrad and Su, Jing and Albrecht-Schmitt, Thomas and Blake, Anastasia and Batista, Enrique and Daly, Scott and Dehnen, Stefanie and Evans, William and Gaunt, Andrew and Kozimor, Stosh and Lichtenberger, Niels and Scott, Brian and Yang, Ping},
abstractNote = {Organometallic synthetic chemistry of transplutonium elements is an area that has been stagnant for decades. Here, we observe the small-scale synthesis, isolated yield, single-crystal X-ray structure, 1H NMR, solution/solid-state UV-vis-nIR spectroscopy, and Density Functional Theory/ab initio Wave Functional Theory calculations on an Am3+ organometallic complex,[Am(C5Me4H)3]. This constitutes the first quantitative data on Am–C bonding in a molecular species.},
doi = {10.1002/anie.201905225},
journal = {Angewandte Chemie (International Edition)},
number = 34,
volume = 58,
place = {United States},
year = {2019},
month = {6}
}

Journal Article:
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This content will become publicly available on June 12, 2020
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Cited by: 2 works
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    Works referencing / citing this record:

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    [An(H2O)9](CF3SO3)3 (An=U-Cm, Cf): Exploring Their Stability, Structural Chemistry, and Magnetic Behavior by Experiment and Theory
    journal, August 2010

    • Apostolidis, Christos; Schimmelpfennig, Bernd; Magnani, Nicola
    • Angewandte Chemie, Vol. 122, Issue 36
    • DOI: 10.1002/ange.201001077

    Die Renaissance der nichtwässrigen Uranchemie
    journal, June 2015


    Comparing the 2,2′-Biphenylenedithiophosphinate Binding of Americium with Neodymium and Europium
    journal, September 2016

    • Cross, Justin N.; Macor, Joseph A.; Bertke, Jeffery A.
    • Angewandte Chemie, Vol. 128, Issue 41
    • DOI: 10.1002/ange.201606367

    A Structurally Characterized Organometallic Plutonium(IV) Complex
    journal, March 2017

    • Apostolidis, Christos; Walter, Olaf; Vogt, Jochen
    • Angewandte Chemie, Vol. 129, Issue 18
    • DOI: 10.1002/ange.201701858

    Tri(cyclopentadienyl)americium(III)
    journal, January 1966

    • Baumgärtner, F.; Fischer, E. O.; Kanellakopulos, B.
    • Angewandte Chemie International Edition in English, Vol. 5, Issue 1
    • DOI: 10.1002/anie.196601342

    [An(H2O)9](CF3SO3)3 (An=U-Cm, Cf): Exploring Their Stability, Structural Chemistry, and Magnetic Behavior by Experiment and Theory
    journal, June 2010

    • Apostolidis, Christos; Schimmelpfennig, Bernd; Magnani, Nicola
    • Angewandte Chemie International Edition, Vol. 49, Issue 36
    • DOI: 10.1002/anie.201001077

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


    Comparing the 2,2′-Biphenylenedithiophosphinate Binding of Americium with Neodymium and Europium
    journal, September 2016

    • Cross, Justin N.; Macor, Joseph A.; Bertke, Jeffery A.
    • Angewandte Chemie International Edition, Vol. 55, Issue 41
    • DOI: 10.1002/anie.201606367

    A Structurally Characterized Organometallic Plutonium(IV) Complex
    journal, March 2017

    • Apostolidis, Christos; Walter, Olaf; Vogt, Jochen
    • Angewandte Chemie International Edition, Vol. 56, Issue 18
    • DOI: 10.1002/anie.201701858

    Solid-State Structure of Tris-Cyclopentadienide Uranium(III) and Plutonium(III)
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    • Apostolidis, Christos; Dutkiewicz, Michał S.; Kovács, Attila
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    • DOI: 10.1002/chem.201704845

    Absorption spectrum of KAm(C8H8)2 in the solution
    journal, January 1977


    The bonding in tris(η5-cyclopentadienyl) actinide complexes IV: Electronic structural effects in AnCl3 and (η5-C5H5)3An (An ≡ Th — Cf) complexes
    journal, April 1989

    • Bursten, Bruce E.; Rhodes, Larry F.; Strittmatter, Richard J.
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    • DOI: 10.1016/0022-5088(89)90487-6

    The magnetic behavior of trivalent americium compounds
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    Bonding, energetic, electronic delocalization and optical properties of MCp3 complexes, where M=Sc, Y, La, Ac, Lu, Ce, Yb and Th
    journal, December 2012


    Organometallic Neptunium Chemistry
    journal, August 2017


    Small-Scale Metal-Based Syntheses of Lanthanide Iodide, Amide, and Cyclopentadienyl Complexes as Analogues for Transuranic Reactions
    journal, September 2017


    Tetramethylcyclopentadienyl Ligands Allow Isolation of Ln(II) Ions across the Lanthanide Series in [K(2.2.2-cryptand)][(C 5 Me 4 H) 3 Ln] Complexes
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    Conversion of Americia to Anhydrous Trivalent Americium Halides
    journal, January 2019


    Recent Developments in Synthesis and Structural Chemistry of Nonaqueous Actinide Complexes
    journal, October 2012

    • Jones, Matthew B.; Gaunt, Andrew J.
    • Chemical Reviews, Vol. 113, Issue 2
    • DOI: 10.1021/cr300198m

    Methyl Displacements from Cyclopentadienyl Ring Planes in Sterically Crowded (C 5 Me 5 ) 3 M Complexes
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    • Evans, William J.; Kozimor, Stosh A.; Ziller, Joseph W.
    • Inorganic Chemistry, Vol. 44, Issue 22
    • DOI: 10.1021/ic051130h

    Synthesis, Structure, and 15 N NMR Studies of Paramagnetic Lanthanide Complexes Obtained by Reduction of Dinitrogen
    journal, December 2006

    • Evans, William J.; Rego, Daniel B.; Ziller, Joseph W.
    • Inorganic Chemistry, Vol. 45, Issue 26
    • DOI: 10.1021/ic061485g

    Paramagnetism of Aqueous Actinide Cations. Part I: Perchloric Acid Media
    journal, February 2014

    • Wall, Thomas F.; Jan, Steve; Autillo, Matthieu
    • Inorganic Chemistry, Vol. 53, Issue 5
    • DOI: 10.1021/ic402371x

    Structural, Spectroscopic, and Theoretical Comparison of Traditional vs Recently Discovered Ln 2+ Ions in the [K(2.2.2-cryptand)][(C 5 H 4 SiMe 3 ) 3 Ln] Complexes: The Variable Nature of Dy 2+ and Nd 2+
    journal, December 2014

    • Fieser, Megan E.; MacDonald, Matthew R.; Krull, Brandon T.
    • Journal of the American Chemical Society, Vol. 137, Issue 1
    • DOI: 10.1021/ja510831n

    Gas-Phase Transuranium Organometallic Chemistry:  Reactions of Np + , Pu + , NpO + , and PuO + with Alkenes
    journal, March 1998

    • Gibson, John K.
    • Journal of the American Chemical Society, Vol. 120, Issue 11
    • DOI: 10.1021/ja973182e

    Identification of the Formal +2 Oxidation State of Plutonium: Synthesis and Characterization of {Pu II [C 5 H 3 (SiMe 3 ) 2 ] 3 }
    journal, March 2017

    • Windorff, Cory J.; Chen, Guo P.; Cross, Justin N.
    • Journal of the American Chemical Society, Vol. 139, Issue 11
    • DOI: 10.1021/jacs.7b00706

    Covalency in Americium(III) Hexachloride
    journal, June 2017

    • Cross, Justin N.; Su, Jing; Batista, Enrique R.
    • Journal of the American Chemical Society, Vol. 139, Issue 25
    • DOI: 10.1021/jacs.7b03755

    Identification of the Formal +2 Oxidation State of Neptunium: Synthesis and Structural Characterization of {Np II [C 5 H 3 (SiMe 3 ) 2 ] 3 } 1–
    journal, May 2018

    • Su, Jing; Windorff, Cory J.; Batista, Enrique R.
    • Journal of the American Chemical Society, Vol. 140, Issue 24
    • DOI: 10.1021/jacs.8b03907

    Americium Organometallic Ions Produced by Laser Ablation of AmO 2 in Polyimide
    journal, June 1998

    • Gibson, John K.
    • The Journal of Physical Chemistry A, Vol. 102, Issue 24
    • DOI: 10.1021/jp981145j

    Gas-Phase Reactions of Americium Ion, Am + , with Alkenes
    journal, June 1998


    Evidence for covalence in a N-donor complex of americium(iii)
    journal, January 2013

    • Adam, Christian; Kaden, Peter; Beele, Björn B.
    • Dalton Transactions, Vol. 42, Issue 39
    • DOI: 10.1039/c3dt50953b

    Absorption Spectrum of Americium Tricyclopentadienide
    journal, July 1969

    • Pappalardo, R.; Carnall, W. T.; Fields, P. R.
    • The Journal of Chemical Physics, Vol. 51, Issue 2
    • DOI: 10.1063/1.1672081