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)

Erickson, K. A.; Kagan, B. D.; Scott, B. L.; Morris, D. E.; Kiplinger, J. L.

doi:10.1039/C7DT02373A

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)

Journal Article · 01 August 2017 · Dalton Transactions

DOI: https://doi.org/10.1039/C7DT02373A · OSTI ID:1402633

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^[2]; Scott, B. L. ^[1]; Morris, D. E. ^[1];

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Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Vermont, Burlington, VT (United States)

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.

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Research Organization:: Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC52-06NA25396

OSTI ID:: 1402633

Report Number(s):: LA--UR-17-23836

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 34 Vol. 46; ISSN 1477-9226; ISSN ICHBD9

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (32)

Synthesis, structure and electrochemical properties of a group of ruthenium(iii) complexes of N-(aryl)picolinamide Das, Anindya; Peng, Shie-Ming; Lee, Gene-Hsiang New Journal of Chemistry, Vol. 28, Issue 6 https://doi.org/10.1039/b317018g	journal	January 2004
Systematic Studies of Early Actinide Complexes: Thorium(IV) Fluoroketimides Schelter, Eric J.; Yang, Ping; Scott, Brian L. Journal of the American Chemical Society, Vol. 129, Issue 16 https://doi.org/10.1021/ja0686458	journal	April 2007
Constrained Geometry Organoactinides as Versatile Catalysts for the Intramolecular Hydroamination/Cyclization of Primary and Secondary Amines Having Diverse Tethered C−C Unsaturation Stubbert, Bryan D.; Marks, Tobin J. Journal of the American Chemical Society, Vol. 129, Issue 14 https://doi.org/10.1021/ja0665444	journal	April 2007
Uranium(IV) bis(amido), imido and bis(acetylide) complexes: synthesis, molecular structure, solution dynamics and interconversion reactions Straub, Thomas; Frank, Walter; Reiss, Guido J. Journal of the Chemical Society, Dalton Transactions, Issue 12 https://doi.org/10.1039/dt9960002541	journal	January 1996
Diamido-Ether Actinide Complexes as Catalysts for the Intramolecular Hydroamination of Aminoalkenes Hayes, Cassandra E.; Platel, Rachel H.; Schafer, Laurel L. Organometallics, Vol. 31, Issue 19 https://doi.org/10.1021/om300410h	journal	September 2012
Trends in Electronic Structure and Redox Energetics for Early-Actinide Pentamethylcyclopentadienyl Complexes Morris, David E.; Da Re, Ryan E.; Jantunen, Kimberly C. Organometallics, Vol. 23, Issue 22 https://doi.org/10.1021/om049634v	journal	October 2004
Novel ring-opening reaction of tetrahydrofuran promoted by a cationic uranium amide compound Boisson, Christophe; Berthet, Jean Claude; Lance, Monique Chemical Communications, Issue 18 https://doi.org/10.1039/cc9960002129	journal	January 1996
Synthesis and Catalytic Characteristics of Novel Constrained-Geometry Organoactinide Catalysts. The First Example of Actinide-Mediated Intramolecular Hydroamination Stubbert, Bryan D.; Stern, Charlotte L.; Marks, Tobin J. Organometallics, Vol. 22, Issue 24 https://doi.org/10.1021/om034093f	journal	November 2003
Synthesis and properties of bis(pentamethylcyclopentadienyl) actinide hydrocarbyls and hydrides. A new class of highly reactive f-element organometallic compounds Fagan, Paul J.; Manriquez, Juan M.; Maatta, Eric A. Journal of the American Chemical Society, Vol. 103, Issue 22 https://doi.org/10.1021/ja00412a021	journal	November 1981
Thorium(IV) and Uranium(IV) Ketimide Complexes Prepared by Nitrile Insertion into Actinide−Alkyl and −Aryl Bonds Jantunen, Kimberly C.; Burns, Carol J.; Castro-Rodriguez, Ingrid Organometallics, Vol. 23, Issue 20 https://doi.org/10.1021/om0343824	journal	September 2004
Catalytic Organic Transformations Mediated by Actinide Complexes Karmel, Isabell; Batrice, Rami; Eisen, Moris Inorganics, Vol. 3, Issue 4 https://doi.org/10.3390/inorganics3040392	journal	October 2015
Organic Compounds of Uranium. II. Uranium(IV) Amides, Alkoxides and Mercaptides Jones, R. G.; Karmas, G.; Martin, G. A. Journal of the American Chemical Society, Vol. 78, Issue 17 https://doi.org/10.1021/ja01598a026	journal	September 1956
Insertion of carbon monoxide into metal-nitrogen bonds. Synthesis, chemistry, structures, and structural dynamics of bis(pentamethylcyclopentadienyl) organoactinide dialkylamides and .eta.2-carbamoyls Fagan, Paul J.; Manriquez, Juan M.; Vollmer, Sarah H. Journal of the American Chemical Society, Vol. 103, Issue 9 https://doi.org/10.1021/ja00399a013	journal	May 1981
Synthesis, structure, spectroscopy and redox energetics of a series of uranium(IV) mixed-ligand metallocene complexes Thomson, Robert K.; Scott, Brian L.; Morris, David E. Comptes Rendus Chimie, Vol. 13, Issue 6-7 https://doi.org/10.1016/j.crci.2010.04.008	journal	June 2010
Synthesis of organouranium( V ) compounds by oxidation of neutral tetravalent precursors. Crystal structures of [U(η-C ₅ Me ₅ )(NMe ₂ ) ₃ (OC ₄ H ₈ )][BPh ₄ ] and [U(η-C ₅ Me ₅ ) ₂ (NEt ₂ ) ₂ ][BPh ₄ ], the first cationic uranium( V ) complexes Boisson, Christophe; Berthet, Jean-Claude; Lance, Monique J. Chem. Soc., Chem. Commun., Issue 5 https://doi.org/10.1039/C39950000543	journal	January 1995
Tetravalent and Pentavalent Uranium Acetylide Complexes Prepared by Oxidative Functionalization with CuCCPh Graves, Christopher R.; Scott, Brian L.; Morris, David E. Organometallics, Vol. 27, Issue 14 https://doi.org/10.1021/om800466m	journal	July 2008
Catalytic Dehydrogenation of Dimethylamine Borane by Highly Active Thorium and Uranium Metallocene Complexes Erickson, Karla A.; Kiplinger, Jaqueline L. ACS Catalysis, Vol. 7, Issue 7 https://doi.org/10.1021/acscatal.7b00967	journal	May 2017
Recent advances in organothorium and organouranium catalysis Andrea, Tamer; Eisen, Moris S. Chem. Soc. Rev., Vol. 37, Issue 3 https://doi.org/10.1039/B614969N	journal	January 2008
Uranium-mediated ring-opening polymerization of ε-caprolactone: a comparative study Karmel, Isabell S. R.; Khononov, Maxim; Tamm, Matthias Catalysis Science & Technology, Vol. 5, Issue 12 https://doi.org/10.1039/C5CY01162K	journal	January 2015
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 Erickson, Karla A.; Scott, Brian L.; Kiplinger, Jaqueline L. Inorganic Chemistry Communications, Vol. 77 https://doi.org/10.1016/j.inoche.2017.01.019	journal	March 2017
Systematic Studies of Early Actinide Complexes: Uranium(IV) Fluoroketimides Schelter, Eric J.; Yang, Ping; Scott, Brian L. Inorganic Chemistry, Vol. 46, Issue 18 https://doi.org/10.1021/ic700455b	journal	September 2007
First uranium(IV) triflates Berthet, Jean Claude; Ephritikhine, Michel; Berthet, Jean Claude Chemical Communications, Issue 13 https://doi.org/10.1039/a801936c	journal	January 1998
Electronic spectra of solid pentakis(dimethylamido)tantalum(V) Kunkely, Horst; Vogler, Arnd Inorganic Chemistry Communications, Vol. 4, Issue 5 https://doi.org/10.1016/S1387-7003(01)00189-7	journal	May 2001
Reactivity of Tuck-in and Tuck-over Uranium Metallocene Complexes Montalvo, Elizabeth; Miller, Kevin A.; Ziller, Joseph W. Organometallics, Vol. 29, Issue 18 https://doi.org/10.1021/om1007538	journal	September 2010
Bis(permethylindenyl) Complexes of Thorium: Synthesis, Structure, and Reactivity Trnka, Tina M.; Bonanno, Jeffrey B.; Bridgewater, Brian M. Organometallics, Vol. 20, Issue 15 https://doi.org/10.1021/om010233e	journal	July 2001
Influence of the 5f Orbitals on the Bonding and Reactivity in Organoactinides: Experimental and Computational Studies on a Uranium Metallacyclopropene Zhang, Lei; Hou, Guohua; Zi, Guofu Journal of the American Chemical Society, Vol. 138, Issue 15 https://doi.org/10.1021/jacs.6b01391	journal	April 2016
Catalytic C–N, C–O, and C–S Bond Formation Promoted by Organoactinide Complexes Eisen, Moris S. C-X Bond Formation https://doi.org/10.1007/978-3-642-12073-2_7	book	January 2010
Exploring the auxiliary co-ordination sphere of tripodal amino(triamido) actinide complexes Scott, Peter; Hitchcock, Peter B. Journal of the Chemical Society, Dalton Transactions, Issue 4 https://doi.org/10.1039/dt9950000603	journal	January 1995
Organoactinides in catalysis Barnea, E.; Eisen, M. Coordination Chemistry Reviews, Vol. 250, Issue 7-8 https://doi.org/10.1016/j.ccr.2005.12.007	journal	April 2006
Synthesis of Organouranium(IV) Triflates from U(OTf)4 or from Alkyl or Amide Precursors Berthet, Jean Claude; Nierlich, Martine; Ephritikhine, Michel European Journal of Inorganic Chemistry, Vol. 2002, Issue 4 https://doi.org/10.1002/1099-0682(200203)2002:4<850::AID-EJIC850>3.0.CO;2-Y	journal	March 2002
Linear and Nonlinear Two-Coordinate Vanadium Complexes: Synthesis, Characterization, and Magnetic Properties of V(II) Amides Boynton, Jessica N.; Guo, Jing-Dong; Fettinger, James C. Journal of the American Chemical Society, Vol. 135, Issue 29 https://doi.org/10.1021/ja403244w	journal	July 2013
Synthesis and reactivity of bis(imido) uranium(vi) cyclopentadienyl complexes Spencer, Liam P.; Gdula, Robyn L.; Hayton, Trevor W. Chemical Communications, Issue 40 https://doi.org/10.1039/b806075d	journal	January 2008

Cited By (1)

A sulphur and uranium fiesta! Synthesis, structure, and characterization of neutral terminal uranium( vi ) monosulphide, uranium( vi ) η ² -disulphide, and uranium( iv ) phosphine sulphide complexes Pagano, Justin K.; Arney, David S. J.; Scott, Brian L. Dalton Transactions, Vol. 48, Issue 1 https://doi.org/10.1039/c8dt02932f	journal	January 2019

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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)

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