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Title: Revisiting the bis(dimethylamido) metallocene complexes of thorium and uranium: improved syntheses, structure, spectroscopy, and redox energetics of (C 5 Me 5 ) 2 An(NMe 2 ) 2 (An = Th, U)

Abstract

In addition to improved syntheses, the solid-state structures, voltammetric data and UV-visible–NIR spectra of (C 5Me 5) 2An(NMe 2) 2(An = Th, U) complexes are presented for the first time.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1];  [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Vermont, Burlington, VT (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1402633
Report Number(s):
LA-UR-17-23836
Journal ID: ISSN 1477-9226; ICHBD9
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 46; Journal Issue: 34; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Erickson, K. A., Kagan, B. D., Scott, B. L., Morris, D. E., and Kiplinger, J. L. Revisiting the bis(dimethylamido) metallocene complexes of thorium and uranium: improved syntheses, structure, spectroscopy, and redox energetics of (C 5 Me 5 ) 2 An(NMe 2 ) 2 (An = Th, U). United States: N. p., 2017. Web. doi:10.1039/C7DT02373A.
Erickson, K. A., Kagan, B. D., Scott, B. L., Morris, D. E., & Kiplinger, J. L. Revisiting the bis(dimethylamido) metallocene complexes of thorium and uranium: improved syntheses, structure, spectroscopy, and redox energetics of (C 5 Me 5 ) 2 An(NMe 2 ) 2 (An = Th, U). United States. doi:10.1039/C7DT02373A.
Erickson, K. A., Kagan, B. D., Scott, B. L., Morris, D. E., and Kiplinger, J. L. Wed . "Revisiting the bis(dimethylamido) metallocene complexes of thorium and uranium: improved syntheses, structure, spectroscopy, and redox energetics of (C 5 Me 5 ) 2 An(NMe 2 ) 2 (An = Th, U)". United States. doi:10.1039/C7DT02373A. https://www.osti.gov/servlets/purl/1402633.
@article{osti_1402633,
title = {Revisiting the bis(dimethylamido) metallocene complexes of thorium and uranium: improved syntheses, structure, spectroscopy, and redox energetics of (C 5 Me 5 ) 2 An(NMe 2 ) 2 (An = Th, U)},
author = {Erickson, K. A. and Kagan, B. D. and Scott, B. L. and Morris, D. E. and Kiplinger, J. L.},
abstractNote = {In addition to improved syntheses, the solid-state structures, voltammetric data and UV-visible–NIR spectra of (C5Me5)2An(NMe2)2(An = Th, U) complexes are presented for the first time.},
doi = {10.1039/C7DT02373A},
journal = {Dalton Transactions},
issn = {1477-9226},
number = 34,
volume = 46,
place = {United States},
year = {2017},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1. Figure 1.: Uranium metallocene complexes with electronically different nitrogen-based donor ligands: bis(imido) (I), bis(ketimido) (II), bis(amido) (III).

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Works referenced in this record:

Novel ring-opening reaction of tetrahydrofuran promoted by a cationic uranium amide compound
journal, January 1996

  • Boisson, Christophe; Berthet, Jean Claude; Lance, Monique
  • Chemical Communications, Issue 18
  • DOI: 10.1039/cc9960002129

Reactivity of Tuck-in and Tuck-over Uranium Metallocene Complexes
journal, September 2010

  • Montalvo, Elizabeth; Miller, Kevin A.; Ziller, Joseph W.
  • Organometallics, Vol. 29, Issue 18
  • DOI: 10.1021/om1007538

First uranium(IV) triflates
journal, January 1998

  • Berthet, Jean Claude; Ephritikhine, Michel; Berthet, Jean Claude
  • Chemical Communications, Issue 13
  • DOI: 10.1039/a801936c

Systematic Studies of Early Actinide Complexes:  Thorium(IV) Fluoroketimides
journal, April 2007

  • Schelter, Eric J.; Yang, Ping; Scott, Brian L.
  • Journal of the American Chemical Society, Vol. 129, Issue 16
  • DOI: 10.1021/ja0686458

Synthesis, structure and electrochemical properties of a group of ruthenium(iii) complexes of N-(aryl)picolinamide
journal, January 2004

  • Das, Anindya; Peng, Shie-Ming; Lee, Gene-Hsiang
  • New Journal of Chemistry, Vol. 28, Issue 6
  • DOI: 10.1039/b317018g

Synthesis of Organouranium(IV) Triflates from U(OTf)4 or from Alkyl or Amide Precursors
journal, March 2002


Tetravalent and Pentavalent Uranium Acetylide Complexes Prepared by Oxidative Functionalization with CuCCPh
journal, July 2008

  • Graves, Christopher R.; Scott, Brian L.; Morris, David E.
  • Organometallics, Vol. 27, Issue 14
  • DOI: 10.1021/om800466m

Electronic spectra of solid pentakis(dimethylamido)tantalum(V)
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Uranium(IV) bis(amido), imido and bis(acetylide) complexes: synthesis, molecular structure, solution dynamics and interconversion reactions
journal, January 1996

  • Straub, Thomas; Frank, Walter; Reiss, Guido J.
  • Journal of the Chemical Society, Dalton Transactions, Issue 12
  • DOI: 10.1039/dt9960002541

Synthesis, structure, spectroscopy and redox energetics of a series of uranium(IV) mixed-ligand metallocene complexes
journal, June 2010


Influence of the 5f Orbitals on the Bonding and Reactivity in Organoactinides: Experimental and Computational Studies on a Uranium Metallacyclopropene
journal, April 2016

  • Zhang, Lei; Hou, Guohua; Zi, Guofu
  • Journal of the American Chemical Society, Vol. 138, Issue 15
  • DOI: 10.1021/jacs.6b01391

Ca(BH4)2 as a simple tool for the preparation of thorium and uranium metallocene borohydride complexes: First synthesis and crystal structure of (C5Me5)2Th(η3-H3BH)2
journal, March 2017

  • Erickson, Karla A.; Scott, Brian L.; Kiplinger, Jaqueline L.
  • Inorganic Chemistry Communications, Vol. 77
  • DOI: 10.1016/j.inoche.2017.01.019

Systematic Studies of Early Actinide Complexes:  Uranium(IV) Fluoroketimides
journal, September 2007

  • Schelter, Eric J.; Yang, Ping; Scott, Brian L.
  • Inorganic Chemistry, Vol. 46, Issue 18
  • DOI: 10.1021/ic700455b

Recent advances in organothorium and organouranium catalysis
journal, January 2008

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Organoactinides in catalysis
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Bis(permethylindenyl) Complexes of Thorium:  Synthesis, Structure, and Reactivity
journal, July 2001

  • Trnka, Tina M.; Bonanno, Jeffrey B.; Bridgewater, Brian M.
  • Organometallics, Vol. 20, Issue 15
  • DOI: 10.1021/om010233e

Catalytic Organic Transformations Mediated by Actinide Complexes
journal, October 2015


Diamido-Ether Actinide Complexes as Catalysts for the Intramolecular Hydroamination of Aminoalkenes
journal, September 2012

  • Hayes, Cassandra E.; Platel, Rachel H.; Schafer, Laurel L.
  • Organometallics, Vol. 31, Issue 19
  • DOI: 10.1021/om300410h

Synthesis and reactivity of bis(imido) uranium(vi) cyclopentadienyl complexes
journal, January 2008

  • Spencer, Liam P.; Gdula, Robyn L.; Hayton, Trevor W.
  • Chemical Communications, Issue 40
  • DOI: 10.1039/b806075d

Linear and Nonlinear Two-Coordinate Vanadium Complexes: Synthesis, Characterization, and Magnetic Properties of V(II) Amides
journal, July 2013

  • Boynton, Jessica N.; Guo, Jing-Dong; Fettinger, James C.
  • Journal of the American Chemical Society, Vol. 135, Issue 29
  • DOI: 10.1021/ja403244w

Exploring the auxiliary co-ordination sphere of tripodal amino(triamido) actinide complexes
journal, January 1995

  • Scott, Peter; Hitchcock, Peter B.
  • Journal of the Chemical Society, Dalton Transactions, Issue 4
  • DOI: 10.1039/dt9950000603

Organic Compounds of Uranium. II. Uranium(IV) Amides, Alkoxides and Mercaptides
journal, September 1956

  • Jones, R. G.; Karmas, G.; Martin, G. A.
  • Journal of the American Chemical Society, Vol. 78, Issue 17
  • DOI: 10.1021/ja01598a026

Synthesis and Catalytic Characteristics of Novel Constrained-Geometry Organoactinide Catalysts. The First Example of Actinide-Mediated Intramolecular Hydroamination
journal, November 2003

  • Stubbert, Bryan D.; Stern, Charlotte L.; Marks, Tobin J.
  • Organometallics, Vol. 22, Issue 24
  • DOI: 10.1021/om034093f

Synthesis and properties of bis(pentamethylcyclopentadienyl) actinide hydrocarbyls and hydrides. A new class of highly reactive f-element organometallic compounds
journal, November 1981

  • Fagan, Paul J.; Manriquez, Juan M.; Maatta, Eric A.
  • Journal of the American Chemical Society, Vol. 103, Issue 22
  • DOI: 10.1021/ja00412a021

Catalytic Dehydrogenation of Dimethylamine Borane by Highly Active Thorium and Uranium Metallocene Complexes
journal, May 2017


Uranium-mediated ring-opening polymerization of ε-caprolactone: a comparative study
journal, January 2015

  • Karmel, Isabell S. R.; Khononov, Maxim; Tamm, Matthias
  • Catalysis Science & Technology, Vol. 5, Issue 12
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Trends in Electronic Structure and Redox Energetics for Early-Actinide Pentamethylcyclopentadienyl Complexes
journal, October 2004

  • Morris, David E.; Da Re, Ryan E.; Jantunen, Kimberly C.
  • Organometallics, Vol. 23, Issue 22
  • DOI: 10.1021/om049634v

Thorium(IV) and Uranium(IV) Ketimide Complexes Prepared by Nitrile Insertion into Actinide−Alkyl and −Aryl Bonds
journal, September 2004

  • Jantunen, Kimberly C.; Burns, Carol J.; Castro-Rodriguez, Ingrid
  • Organometallics, Vol. 23, Issue 20
  • DOI: 10.1021/om0343824

    Works referencing / citing this record:

    Organoactinides in catalysis
    journal, April 2006


    Synthesis, structure, spectroscopy and redox energetics of a series of uranium(IV) mixed-ligand metallocene complexes
    journal, June 2010


    Ca(BH4)2 as a simple tool for the preparation of thorium and uranium metallocene borohydride complexes: First synthesis and crystal structure of (C5Me5)2Th(η3-H3BH)2
    journal, March 2017

    • Erickson, Karla A.; Scott, Brian L.; Kiplinger, Jaqueline L.
    • Inorganic Chemistry Communications, Vol. 77
    • DOI: 10.1016/j.inoche.2017.01.019

    Catalytic Dehydrogenation of Dimethylamine Borane by Highly Active Thorium and Uranium Metallocene Complexes
    journal, May 2017


    Systematic Studies of Early Actinide Complexes:  Uranium(IV) Fluoroketimides
    journal, September 2007

    • Schelter, Eric J.; Yang, Ping; Scott, Brian L.
    • Inorganic Chemistry, Vol. 46, Issue 18
    • DOI: 10.1021/ic700455b

    Synthesis and properties of bis(pentamethylcyclopentadienyl) actinide hydrocarbyls and hydrides. A new class of highly reactive f-element organometallic compounds
    journal, November 1981

    • Fagan, Paul J.; Manriquez, Juan M.; Maatta, Eric A.
    • Journal of the American Chemical Society, Vol. 103, Issue 22
    • DOI: 10.1021/ja00412a021

    Organic Compounds of Uranium. II. Uranium(IV) Amides, Alkoxides and Mercaptides
    journal, September 1956

    • Jones, R. G.; Karmas, G.; Martin, G. A.
    • Journal of the American Chemical Society, Vol. 78, Issue 17
    • DOI: 10.1021/ja01598a026

    Systematic Studies of Early Actinide Complexes:  Thorium(IV) Fluoroketimides
    journal, April 2007

    • Schelter, Eric J.; Yang, Ping; Scott, Brian L.
    • Journal of the American Chemical Society, Vol. 129, Issue 16
    • DOI: 10.1021/ja0686458

    Linear and Nonlinear Two-Coordinate Vanadium Complexes: Synthesis, Characterization, and Magnetic Properties of V(II) Amides
    journal, July 2013

    • Boynton, Jessica N.; Guo, Jing-Dong; Fettinger, James C.
    • Journal of the American Chemical Society, Vol. 135, Issue 29
    • DOI: 10.1021/ja403244w

    Influence of the 5f Orbitals on the Bonding and Reactivity in Organoactinides: Experimental and Computational Studies on a Uranium Metallacyclopropene
    journal, April 2016

    • Zhang, Lei; Hou, Guohua; Zi, Guofu
    • Journal of the American Chemical Society, Vol. 138, Issue 15
    • DOI: 10.1021/jacs.6b01391

    Bis(permethylindenyl) Complexes of Thorium:  Synthesis, Structure, and Reactivity
    journal, July 2001

    • Trnka, Tina M.; Bonanno, Jeffrey B.; Bridgewater, Brian M.
    • Organometallics, Vol. 20, Issue 15
    • DOI: 10.1021/om010233e

    Synthesis and Catalytic Characteristics of Novel Constrained-Geometry Organoactinide Catalysts. The First Example of Actinide-Mediated Intramolecular Hydroamination
    journal, November 2003

    • Stubbert, Bryan D.; Stern, Charlotte L.; Marks, Tobin J.
    • Organometallics, Vol. 22, Issue 24
    • DOI: 10.1021/om034093f

    Thorium(IV) and Uranium(IV) Ketimide Complexes Prepared by Nitrile Insertion into Actinide−Alkyl and −Aryl Bonds
    journal, September 2004

    • Jantunen, Kimberly C.; Burns, Carol J.; Castro-Rodriguez, Ingrid
    • Organometallics, Vol. 23, Issue 20
    • DOI: 10.1021/om0343824

    Trends in Electronic Structure and Redox Energetics for Early-Actinide Pentamethylcyclopentadienyl Complexes
    journal, October 2004

    • Morris, David E.; Da Re, Ryan E.; Jantunen, Kimberly C.
    • Organometallics, Vol. 23, Issue 22
    • DOI: 10.1021/om049634v

    Reactivity of Tuck-in and Tuck-over Uranium Metallocene Complexes
    journal, September 2010

    • Montalvo, Elizabeth; Miller, Kevin A.; Ziller, Joseph W.
    • Organometallics, Vol. 29, Issue 18
    • DOI: 10.1021/om1007538

    Diamido-Ether Actinide Complexes as Catalysts for the Intramolecular Hydroamination of Aminoalkenes
    journal, September 2012

    • Hayes, Cassandra E.; Platel, Rachel H.; Schafer, Laurel L.
    • Organometallics, Vol. 31, Issue 19
    • DOI: 10.1021/om300410h

    Tetravalent and Pentavalent Uranium Acetylide Complexes Prepared by Oxidative Functionalization with CuCCPh
    journal, July 2008

    • Graves, Christopher R.; Scott, Brian L.; Morris, David E.
    • Organometallics, Vol. 27, Issue 14
    • DOI: 10.1021/om800466m

    First uranium(IV) triflates
    journal, January 1998

    • Berthet, Jean Claude; Ephritikhine, Michel; Berthet, Jean Claude
    • Chemical Communications, Issue 13
    • DOI: 10.1039/a801936c

    Synthesis, structure and electrochemical properties of a group of ruthenium(iii) complexes of N-(aryl)picolinamide
    journal, January 2004

    • Das, Anindya; Peng, Shie-Ming; Lee, Gene-Hsiang
    • New Journal of Chemistry, Vol. 28, Issue 6
    • DOI: 10.1039/b317018g

    Synthesis and reactivity of bis(imido) uranium(vi) cyclopentadienyl complexes
    journal, January 2008

    • Spencer, Liam P.; Gdula, Robyn L.; Hayton, Trevor W.
    • Chemical Communications, Issue 40
    • DOI: 10.1039/b806075d

    Novel ring-opening reaction of tetrahydrofuran promoted by a cationic uranium amide compound
    journal, January 1996

    • Boisson, Christophe; Berthet, Jean Claude; Lance, Monique
    • Chemical Communications, Issue 18
    • DOI: 10.1039/cc9960002129

    Exploring the auxiliary co-ordination sphere of tripodal amino(triamido) actinide complexes
    journal, January 1995

    • Scott, Peter; Hitchcock, Peter B.
    • Journal of the Chemical Society, Dalton Transactions, Issue 4
    • DOI: 10.1039/dt9950000603

    Uranium(IV) bis(amido), imido and bis(acetylide) complexes: synthesis, molecular structure, solution dynamics and interconversion reactions
    journal, January 1996

    • Straub, Thomas; Frank, Walter; Reiss, Guido J.
    • Journal of the Chemical Society, Dalton Transactions, Issue 12
    • DOI: 10.1039/dt9960002541

    Catalytic Organic Transformations Mediated by Actinide Complexes
    journal, October 2015


      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.