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Title: Uranium(III)-carbon multiple bonding supported by arene δ-bonding in mixed-valence hexauranium nanometre-scale rings

Abstract

Despite the fact that non-aqueous uranium chemistry is over 60 years old, most polarised-covalent uranium-element multiple bonds involve formal uranium oxidation states IV, V, and VI. The paucity of uranium(III) congeners is because, in common with metal-ligand multiple bonding generally, such linkages involve strongly donating, charge-loaded ligands that bind best to electron-poor metals and inherently promote disproportionation of uranium(III). Here, we report the synthesis of hexauranium-methanediide nanometre-scale rings. Combined experimental and computational studies suggest overall the presence of formal uranium(III) and (IV) ions, though electron delocalisation in this Kramers system cannot be definitively ruled out, and the resulting polarised-covalent U = C bonds are supported by iodide and δ-bonded arene bridges. The arenes provide reservoirs that accommodate charge, thus avoiding inter-electronic repulsion that would destabilise these low oxidation state metal-ligand multiple bonds. Using arenes as electronic buffers could constitute a general synthetic strategy by which to stabilise otherwise inherently unstable metal-ligand linkages.

Authors:
 [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [1];  [1];  [2];  [2]; ORCiD logo [3];  [4]; ORCiD logo [4]; ORCiD logo [1]
  1. Univ. of Manchester (United Kingdom)
  2. Australian National Univ., Canberra, ACT (Australia)
  3. Univ. of Nottingham (United Kingdom)
  4. Univ. of Minnesota, Minneapolis, MN (United States)
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1506462
Grant/Contract Number:  
SC0002183
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY

Citation Formats

Wooles, Ashley J., Mills, David P., Tuna, Floriana, McInnes, Eric J. L., Law, Gareth T. W., Fuller, Adam J., Kremer, Felipe, Ridgway, Mark, Lewis, William, Gagliardi, Laura, Vlaisavljevich, Bess, and Liddle, Stephen T. Uranium(III)-carbon multiple bonding supported by arene δ-bonding in mixed-valence hexauranium nanometre-scale rings. United States: N. p., 2018. Web. doi:10.1038/s41467-018-04560-7.
Wooles, Ashley J., Mills, David P., Tuna, Floriana, McInnes, Eric J. L., Law, Gareth T. W., Fuller, Adam J., Kremer, Felipe, Ridgway, Mark, Lewis, William, Gagliardi, Laura, Vlaisavljevich, Bess, & Liddle, Stephen T. Uranium(III)-carbon multiple bonding supported by arene δ-bonding in mixed-valence hexauranium nanometre-scale rings. United States. doi:10.1038/s41467-018-04560-7.
Wooles, Ashley J., Mills, David P., Tuna, Floriana, McInnes, Eric J. L., Law, Gareth T. W., Fuller, Adam J., Kremer, Felipe, Ridgway, Mark, Lewis, William, Gagliardi, Laura, Vlaisavljevich, Bess, and Liddle, Stephen T. Tue . "Uranium(III)-carbon multiple bonding supported by arene δ-bonding in mixed-valence hexauranium nanometre-scale rings". United States. doi:10.1038/s41467-018-04560-7. https://www.osti.gov/servlets/purl/1506462.
@article{osti_1506462,
title = {Uranium(III)-carbon multiple bonding supported by arene δ-bonding in mixed-valence hexauranium nanometre-scale rings},
author = {Wooles, Ashley J. and Mills, David P. and Tuna, Floriana and McInnes, Eric J. L. and Law, Gareth T. W. and Fuller, Adam J. and Kremer, Felipe and Ridgway, Mark and Lewis, William and Gagliardi, Laura and Vlaisavljevich, Bess and Liddle, Stephen T.},
abstractNote = {Despite the fact that non-aqueous uranium chemistry is over 60 years old, most polarised-covalent uranium-element multiple bonds involve formal uranium oxidation states IV, V, and VI. The paucity of uranium(III) congeners is because, in common with metal-ligand multiple bonding generally, such linkages involve strongly donating, charge-loaded ligands that bind best to electron-poor metals and inherently promote disproportionation of uranium(III). Here, we report the synthesis of hexauranium-methanediide nanometre-scale rings. Combined experimental and computational studies suggest overall the presence of formal uranium(III) and (IV) ions, though electron delocalisation in this Kramers system cannot be definitively ruled out, and the resulting polarised-covalent U = C bonds are supported by iodide and δ-bonded arene bridges. The arenes provide reservoirs that accommodate charge, thus avoiding inter-electronic repulsion that would destabilise these low oxidation state metal-ligand multiple bonds. Using arenes as electronic buffers could constitute a general synthetic strategy by which to stabilise otherwise inherently unstable metal-ligand linkages.},
doi = {10.1038/s41467-018-04560-7},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {5}
}

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Figures / Tables:

Fig. 1 Fig. 1: Synthesis of complexes 2, 3, and 4 along with definitions of computational models used in this study. See ref. 43 for the synthesis of complex 2

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Works referenced in this record:

Uranium-Carbon Multiple Bonding: Facile Access to the Pentavalent Uranium Carbene [U{C(PPh 2 NSiMe 3 ) 2 }(Cl) 2 (I)] and Comparison of U V C and U IV C Bonds
journal, February 2011

  • Cooper, Oliver J.; Mills, David P.; McMaster, Jonathan
  • Angewandte Chemie International Edition, Vol. 50, Issue 10
  • DOI: 10.1002/anie.201007675

A Monometallic f Element Complex of Dinitrogen:  (C 5 Me 5 ) 3 U(η 1 -N 2 )
journal, November 2003

  • Evans, William J.; Kozimor, Stosh A.; Ziller, Joseph W.
  • Journal of the American Chemical Society, Vol. 125, Issue 47
  • DOI: 10.1021/ja037647e

Probing the 5f Orbital Contribution to the Bonding in a U(V) Ketimide Complex
journal, February 2012

  • Seaman, Lani A.; Wu, Guang; Edelstein, Norman
  • Journal of the American Chemical Society, Vol. 134, Issue 10
  • DOI: 10.1021/ja211875s

A uranium-carbon multiple bond. Crystal and molecular structure of (.eta.5-C5H5)3UCHP(CH3)2(C6H5)
journal, June 1981

  • Cramer, Roger E.; Maynard, Richard B.; Paw, Josephine C.
  • Journal of the American Chemical Society, Vol. 103, Issue 12
  • DOI: 10.1021/ja00402a065

Reactions of Actinide Metal Atoms with Ethane: Computation and Observation of New Th and U Ethylidene Dihydride, Metallacyclopropane Dihydride, and Vinyl Metal Trihydride Complexes
journal, July 2008

  • Cho, Han-Gook; Lyon, Jonathan T.; Andrews, Lester
  • The Journal of Physical Chemistry A, Vol. 112, Issue 30
  • DOI: 10.1021/jp801692s

A Theoretical Study of Uranium(IV) Bis-Methyl Complexes: Towards the Predictive Formation of a Transient Uranium(IV) Carbene Complex
journal, April 2010

  • Yahia, Ahmed; Castro, Ludovic; Maron, Laurent
  • Chemistry - A European Journal, Vol. 16, Issue 19
  • DOI: 10.1002/chem.201000022

Siloxides as Supporting Ligands in Uranium(III)-Mediated Small-Molecule Activation
journal, November 2012

  • Mougel, Victor; Camp, Clément; Pécaut, Jacques
  • Angewandte Chemie International Edition, Vol. 51, Issue 49
  • DOI: 10.1002/anie.201206955

Actinide covalency measured by pulsed electron paramagnetic resonance spectroscopy
journal, December 2016

  • Formanuik, Alasdair; Ariciu, Ana-Maria; Ortu, Fabrizio
  • Nature Chemistry, Vol. 9, Issue 6
  • DOI: 10.1038/nchem.2692

Synthesis of a Phosphorano-Stabilized U(IV)-Carbene via One-Electron Oxidation of a U(III)-Ylide Adduct
journal, May 2011

  • Fortier, Skye; Walensky, Justin R.; Wu, Guang
  • Journal of the American Chemical Society, Vol. 133, Issue 18
  • DOI: 10.1021/ja2001133

Investigation of the Electronic Ground States for a Reduced Pyridine(diimine) Uranium Series: Evidence for a Ligand Tetraanion Stabilized by a Uranium Dimer
journal, April 2015

  • Anderson, Nickolas H.; Odoh, Samuel O.; Williams, Ursula J.
  • Journal of the American Chemical Society, Vol. 137, Issue 14
  • DOI: 10.1021/ja511867a

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

Uranium carbene compounds
journal, April 2013


Infrared Spectrum and Bonding in Uranium Methylidene Dihydride, CH 2 UH 2
journal, June 2007

  • Lyon, Jonathan T.; Andrews, Lester; Malmqvist, Per-Åke
  • Inorganic Chemistry, Vol. 46, Issue 12
  • DOI: 10.1021/ic062407w

Magnetic Susceptibility of Uranium Complexes
journal, August 2014

  • Kindra, Douglas R.; Evans, William J.
  • Chemical Reviews, Vol. 114, Issue 18
  • DOI: 10.1021/cr500242w

Preparation of the first molecular carbon monoxide complex of uranium, (Me3SiC5H4)3UCO
journal, January 1986

  • Brennan, John G.; Andersen, Richard A.; Robbins, John L.
  • Journal of the American Chemical Society, Vol. 108, Issue 2
  • DOI: 10.1021/ja00262a046

Formation and Characterization of the Uranium Methylidene Complexes CH 2 UHX (X = F, Cl, and Br)
journal, February 2006

  • Lyon, Jonathan T.; Andrews, Lester
  • Inorganic Chemistry, Vol. 45, Issue 4
  • DOI: 10.1021/ic051785i

Exploring the Uranyl Organometallic Chemistry: From Single to Double Uranium−Carbon Bonds
journal, April 2011

  • Tourneux, Jean-Christophe; Berthet, Jean-Claude; Cantat, Thibault
  • Journal of the American Chemical Society, Vol. 133, Issue 16
  • DOI: 10.1021/ja201276h

The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes
journal, February 2017

  • Gregson, Matthew; Lu, Erli; Mills, David P.
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14137

Investigations of the Electronic Structure of Arene-Bridged Diuranium Complexes
journal, January 2013

  • Vlaisavljevich, Bess; Diaconescu, Paula L.; Lukens, Wayne L.
  • Organometallics, Vol. 32, Issue 5
  • DOI: 10.1021/om3010367

Synthesis and Characterization of a Uranium(II) Monoarene Complex Supported by δ  Backbonding
journal, May 2014

  • La Pierre, Henry S.; Scheurer, Andreas; Heinemann, Frank W.
  • Angewandte Chemie International Edition, Vol. 53, Issue 28
  • DOI: 10.1002/anie.201402050

Molecular Octa-Uranium Rings with Alternating Nitride and Azide Bridges
journal, September 2005


Comparative Study of f-Element Electronic Structure across a Series of Multimetallic Actinide and Lanthanoid-Actinide Complexes Possessing Redox-Active Bridging Ligands
journal, February 2010

  • Schelter, Eric J.; Wu, Ruilian; Veauthier, Jacqueline M.
  • Inorganic Chemistry, Vol. 49, Issue 4
  • DOI: 10.1021/ic9024475

Emergence of comparable covalency in isostructural cerium( iv )– and uranium( iv )–carbon multiple bonds
journal, January 2016

  • Gregson, Matthew; Lu, Erli; Tuna, Floriana
  • Chemical Science, Vol. 7, Issue 5
  • DOI: 10.1039/C6SC00278A

Uranium(IV) Nucleophilic Carbene Complexes
journal, June 2011

  • Tourneux, Jean-Christophe; Berthet, Jean-Claude; Cantat, Thibault
  • Organometallics, Vol. 30, Issue 11
  • DOI: 10.1021/om200006g

Synthesis and Characterization of N-Heterocyclic Carbene Complexes of Uranium(III)
journal, February 2004

  • Nakai, Hidetaka; Hu, Xile; Zakharov, Lev N.
  • Inorganic Chemistry, Vol. 43, Issue 3
  • DOI: 10.1021/ic035142j

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


Synthesis and Single Crystal X-ray Diffraction Study on the First Isolable Carbonyl Complex of an Actinide, (C5Me4H)3U(CO)
journal, March 1995

  • Parry, Julian; Carmona, Ernesto; Coles, Simon
  • Journal of the American Chemical Society, Vol. 117, Issue 9
  • DOI: 10.1021/ja00114a030

Quantifying the σ and π Interactions between U(V) f Orbitals and Halide, Alkyl, Alkoxide, Amide and Ketimide Ligands
journal, July 2013

  • Lukens, Wayne W.; Edelstein, Norman M.; Magnani, Nicola
  • Journal of the American Chemical Society, Vol. 135, Issue 29
  • DOI: 10.1021/ja403815h

Uranium-carbon multiple bond chemistry. 2. Coupling of bridging and terminal carbonyls in the formation of an iron .eta.1:.eta.3-allyl complex
journal, October 1983

  • Cramer, Roger E.; Higa, Kelvin T.; Pruskin, Steven L.
  • Journal of the American Chemical Society, Vol. 105, Issue 22
  • DOI: 10.1021/ja00360a052

Comparative Reactivity of Sterically Crowded nf 3 (C 5 Me 5 ) 3 Nd and (C 5 Me 5 ) 3 U Complexes with CO:  Formation of a Nonclassical Carbonium Ion versus an f Element Metal Carbonyl Complex
journal, November 2003

  • Evans, William J.; Kozimor, Stosh A.; Nyce, Gregory W.
  • Journal of the American Chemical Society, Vol. 125, Issue 45
  • DOI: 10.1021/ja036631l

Synthesis and Structure of Nitride-Bridged Uranium(III) Complexes
journal, February 2016

  • Chatelain, Lucile; Scopelliti, Rosario; Mazzanti, Marinella
  • Journal of the American Chemical Society, Vol. 138, Issue 6
  • DOI: 10.1021/jacs.5b12620

Incipient class II mixed valency in a plutonium solid-state compound
journal, May 2017

  • Cary, Samantha K.; Galley, Shane S.; Marsh, Matthew L.
  • Nature Chemistry, Vol. 9, Issue 9
  • DOI: 10.1038/nchem.2777

Identification of the +2 Oxidation State for Uranium in a Crystalline Molecular Complex, [K(2.2.2-Cryptand)][(C 5 H 4 SiMe 3 ) 3 U]
journal, August 2013

  • MacDonald, Matthew R.; Fieser, Megan E.; Bates, Jefferson E.
  • Journal of the American Chemical Society, Vol. 135, Issue 36
  • DOI: 10.1021/ja406791t

Isocyanide Insertion into a Uranium-Carbon Double Bond
journal, November 1984

  • Cramer, Roger E.; Panchanatheswaran, K.; Gilje, John W.
  • Angewandte Chemie International Edition in English, Vol. 23, Issue 11
  • DOI: 10.1002/anie.198409121

Rare-Earth- and Uranium-Mesoionic Carbenes: A New Class of f-Block Carbene Complex Derived from an N-Heterocyclic Olefin
journal, August 2017

  • Seed, John A.; Gregson, Matthew; Tuna, Floriana
  • Angewandte Chemie International Edition, Vol. 56, Issue 38
  • DOI: 10.1002/anie.201706546

Trends in Covalency for d- and f-Element Metallocene Dichlorides Identified Using Chlorine K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory
journal, September 2009

  • Kozimor, Stosh A.; Yang, Ping; Batista, Enrique R.
  • Journal of the American Chemical Society, Vol. 131, Issue 34
  • DOI: 10.1021/ja9015759

Mixed Valency in a Uranium Multimetallic Complex
journal, April 2008

  • Schelter, Eric J.; Wu, Ruilian; Scott, Brian L.
  • Angewandte Chemie International Edition, Vol. 47, Issue 16
  • DOI: 10.1002/anie.200705781

Metal–ligand multiple bonding in uranium: structure and reactivity
journal, January 2010


Uranium-carbon multiple-bond chemistry. 4. Addition of coordinated carbon monoxide across a uranium-carbon multiple bond
journal, November 1984

  • Cramer, Roger E.; Higa, Kelvin T.; Gilje, John W.
  • Journal of the American Chemical Society, Vol. 106, Issue 23
  • DOI: 10.1021/ja00335a065

Tetrahalide Complexes of the [U(NR) 2 ] 2+ Ion: Synthesis, Theory, and Chlorine K-Edge X-ray Absorption Spectroscopy
journal, January 2013

  • Spencer, Liam P.; Yang, Ping; Minasian, Stefan G.
  • Journal of the American Chemical Society, Vol. 135, Issue 6
  • DOI: 10.1021/ja310575j

Arene-Bridged Diuranium Complexes:  Inverted Sandwiches Supported by δ Backbonding
journal, June 2000

  • Diaconescu, Paula L.; Arnold, Polly L.; Baker, Thomas A.
  • Journal of the American Chemical Society, Vol. 122, Issue 25
  • DOI: 10.1021/ja994484e

A Formal High Oxidation State Inverse-Sandwich Diuranium Complex: A New Route to f-Block-Metal Bonds
journal, September 2011

  • Patel, Dipti; Moro, Fabrizio; McMaster, Jonathan
  • Angewandte Chemie International Edition, Vol. 50, Issue 44
  • DOI: 10.1002/anie.201104110

Structure, Reactivity, and Density Functional Theory Analysis of the Six-Electron Reductant, [(C 5 Me 5 ) 2 U] 2- η 66 -C 6 H 6 ), Synthesized via a New Mode of (C 5 Me 5 ) 3 M Reactivity
journal, November 2004

  • Evans, William J.; Kozimor, Stosh A.; Ziller, Joseph W.
  • Journal of the American Chemical Society, Vol. 126, Issue 44
  • DOI: 10.1021/ja0463886

The role of the 5f valence orbitals of early actinides in chemical bonding
journal, July 2017

  • Vitova, T.; Pidchenko, I.; Fellhauer, D.
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms16053

Covalent Uranium Carbene Chemistry
journal, March 2015


Synthesis, Structure, and Magnetism of an f Element Nitrosyl Complex, (C 5 Me 4 H) 3 UNO
journal, December 2011

  • Siladke, Nathan A.; Meihaus, Katie R.; Ziller, Joseph W.
  • Journal of the American Chemical Society, Vol. 134, Issue 2
  • DOI: 10.1021/ja2096128

Agostic Interaction in the Methylidene Metal Dihydride Complexes H 2 MCH 2 (M = Y, Zr, Nb, Mo, Ru, Th, or U)
journal, July 2007

  • Roos, Björn O.; Lindh, Roland; Cho, Han-Gook
  • The Journal of Physical Chemistry A, Vol. 111, Issue 28
  • DOI: 10.1021/jp071914b

Supported organoactinides. Surface chemistry and catalytic properties of alumina-bound cyclopentadienyl and pentamethylcyclopentadienyl thorium and uranium hydrocarbyls and hydrides
journal, February 1985

  • He, Ming Yuan; Xiong, Guoxing; Toscano, Paul J.
  • Journal of the American Chemical Society, Vol. 107, Issue 3
  • DOI: 10.1021/ja00289a016

Early metal bis(phosphorus-stabilised)carbene chemistry
journal, January 2011

  • Liddle, Stephen T.; Mills, David P.; Wooles, Ashley J.
  • Chemical Society Reviews, Vol. 40, Issue 5
  • DOI: 10.1039/c0cs00135j

Description of conjugation and hyperconjugation in terms of electron distributions
journal, July 1983

  • Bader, R. F. W.; Slee, T. S.; Cremer, D.
  • Journal of the American Chemical Society, Vol. 105, Issue 15
  • DOI: 10.1021/ja00353a035

Evidence for the Existence of Group 3 Terminal Methylidene Complexes
journal, July 2016


Uranium carbon multiple-bond chemistry. 3. Insertion of acetonitrile and the formation of a uranium nitrogen multiple bond
journal, March 1984

  • Cramer, Roger E.; Panchanatheswaran, K.; Gilje, John W.
  • Journal of the American Chemical Society, Vol. 106, Issue 6
  • DOI: 10.1021/ja00318a059

The Nature of the UC Double Bond: Pushing the Stability of High-Oxidation-State Uranium Carbenes to the Limit
journal, April 2013

  • Cooper, Oliver J.; Mills, David P.; McMaster, Jonathan
  • Chemistry - A European Journal, Vol. 19, Issue 22
  • DOI: 10.1002/chem.201300071

Formation of Methane versus Benzene in the Reactions of (C 5 Me 5 ) 2 Th(CH 3 ) 2 with [CH 3 PPh 3 ]X (X=Cl, Br, I) Yielding Thorium-Carbene or Thorium-Ylide Complexes
journal, September 2017

  • Rungthanaphatsophon, Pokpong; Bathelier, Adrien; Castro, Ludovic
  • Angewandte Chemie International Edition, Vol. 56, Issue 42
  • DOI: 10.1002/anie.201706496

Synthesis, Thermochemistry, Bonding, and 13 C NMR Chemical Shift Analysis of a Phosphorano-Stabilized Carbene of Thorium
journal, April 2017


Synthesis and structure of [U{C(PPh2NMes)2}2] (Mes = 2,4,6-Me3C6H2): A homoleptic uranium bis(carbene) complex with two formal UC double bonds
journal, January 2010

  • Cooper, Oliver J.; McMaster, Jonathan; Lewis, William
  • Dalton Transactions, Vol. 39, Issue 21
  • DOI: 10.1039/c0dt00152j

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


Multicoordinate ligands for actinide/lanthanide separations
journal, January 2007

  • Dam, Henk H.; Reinhoudt, David N.; Verboom, Willem
  • Chem. Soc. Rev., Vol. 36, Issue 2
  • DOI: 10.1039/B603847F

Dinuclear Trivalent and Mixed-Valence Uranium [(−CH 2 −) 5 ] 4 -calix[4]tetrapyrrole Complexes with Short Intermetallic Distances
journal, December 2001

  • Korobkov, Ilia; Gambarotta, Sandro; Yap, Glenn P. A.
  • Organometallics, Vol. 20, Issue 25
  • DOI: 10.1021/om010510h

The first example of a mixed valence ternary compound of silver with random distribution of Ag( i ) and Ag( ii ) cations
journal, January 2015

  • Mazej, Zoran; Michałowski, Tomasz; Goreshnik, Evgeny A.
  • Dalton Transactions, Vol. 44, Issue 24
  • DOI: 10.1039/C5DT00740B

Small molecule activation at uranium coordination complexes: control of reactivity via molecular architecture
journal, January 2006

  • Castro-Rodríguez, Ingrid; Meyer, Karsten
  • Chemical Communications, Issue 13
  • DOI: 10.1039/b513755c

A mixed-valence uranium(III/IV) bimetallic; structure, magnetism and reactivity
journal, January 1996

  • Roussel, Paul; Hitchcock, Peter B.; Tinker, Nigel
  • Chemical Communications, Issue 17
  • DOI: 10.1039/cc9960002053

The UC Double Bond: Synthesis and Study of Uranium Nucleophilic Carbene Complexes
journal, January 2009

  • Cantat, Thibault; Arliguie, Thérèse; Noël, Anne
  • Journal of the American Chemical Society, Vol. 131, Issue 3
  • DOI: 10.1021/ja807282s

Inverted sandwich arene complexes of uranium
journal, June 2015


Infrared Spectra and Electronic Structures of Agostic Uranium Methylidene Molecules
journal, March 2008

  • Lyon, Jonathan T.; Andrews, Lester; Hu, Han-Shi
  • Inorganic Chemistry, Vol. 47, Issue 5
  • DOI: 10.1021/ic701786h

A delocalized arene-bridged diuranium single-molecule magnet
journal, April 2011

  • Mills, David P.; Moro, Fabrizio; McMaster, Jonathan
  • Nature Chemistry, Vol. 3, Issue 6
  • DOI: 10.1038/nchem.1028

Synthesis, Characterization, and Reactivity of a Uranium(VI) Carbene Imido Oxo Complex
journal, May 2014

  • Lu, Erli; Cooper, Oliver J.; McMaster, Jonathan
  • Angewandte Chemie International Edition, Vol. 53, Issue 26
  • DOI: 10.1002/anie.201403892

Multiconfigurational Second-Order Perturbation Theory Restricted Active Space (RASPT2) Method for Electronic Excited States: A Benchmark Study
journal, December 2010

  • Sauri, Vicenta; Serrano-Andrés, Luis; Shahi, Abdul Rehaman Moughal
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 1
  • DOI: 10.1021/ct100478d

Easy access to uranium nucleophilic carbene complexes
journal, January 2010

  • Tourneux, Jean-Christophe; Berthet, Jean-Claude; Thuéry, Pierre
  • Dalton Transactions, Vol. 39, Issue 10
  • DOI: 10.1039/b926718m

Oxidation State Delineation via U L III -Edge XANES in a Series of Isostructural Uranium Coordination Complexes
journal, April 2012

  • Kosog, Boris; La Pierre, Henry S.; Denecke, Melissa A.
  • Inorganic Chemistry, Vol. 51, Issue 14
  • DOI: 10.1021/ic3011234

    Works referencing / citing this record:

    CCDC 1581465: Experimental Crystal Structure Determination
    dataset, January 2018


    CCDC 1581466: Experimental Crystal Structure Determination
    dataset, January 2018


    Isocyanide Insertion into a Uranium-Carbon Double Bond
    journal, November 1984

    • Cramer, Roger E.; Panchanatheswaran, K.; Gilje, John W.
    • Angewandte Chemie International Edition in English, Vol. 23, Issue 11
    • DOI: 10.1002/anie.198409121

    Mixed Valency in a Uranium Multimetallic Complex
    journal, April 2008

    • Schelter, Eric J.; Wu, Ruilian; Scott, Brian L.
    • Angewandte Chemie International Edition, Vol. 47, Issue 16
    • DOI: 10.1002/anie.200705781

    Uranium-Carbon Multiple Bonding: Facile Access to the Pentavalent Uranium Carbene [U{C(PPh 2 NSiMe 3 ) 2 }(Cl) 2 (I)] and Comparison of U V C and U IV C Bonds
    journal, February 2011

    • Cooper, Oliver J.; Mills, David P.; McMaster, Jonathan
    • Angewandte Chemie International Edition, Vol. 50, Issue 10
    • DOI: 10.1002/anie.201007675

    A Formal High Oxidation State Inverse-Sandwich Diuranium Complex: A New Route to f-Block-Metal Bonds
    journal, September 2011

    • Patel, Dipti; Moro, Fabrizio; McMaster, Jonathan
    • Angewandte Chemie International Edition, Vol. 50, Issue 44
    • DOI: 10.1002/anie.201104110

    Siloxides as Supporting Ligands in Uranium(III)-Mediated Small-Molecule Activation
    journal, November 2012

    • Mougel, Victor; Camp, Clément; Pécaut, Jacques
    • Angewandte Chemie International Edition, Vol. 51, Issue 49
    • DOI: 10.1002/anie.201206955

    Synthesis and Characterization of a Uranium(II) Monoarene Complex Supported by δ  Backbonding
    journal, May 2014

    • La Pierre, Henry S.; Scheurer, Andreas; Heinemann, Frank W.
    • Angewandte Chemie International Edition, Vol. 53, Issue 28
    • DOI: 10.1002/anie.201402050

    Synthesis, Characterization, and Reactivity of a Uranium(VI) Carbene Imido Oxo Complex
    journal, May 2014

    • Lu, Erli; Cooper, Oliver J.; McMaster, Jonathan
    • Angewandte Chemie International Edition, Vol. 53, Issue 26
    • DOI: 10.1002/anie.201403892

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


    Formation of Methane versus Benzene in the Reactions of (C 5 Me 5 ) 2 Th(CH 3 ) 2 with [CH 3 PPh 3 ]X (X=Cl, Br, I) Yielding Thorium-Carbene or Thorium-Ylide Complexes
    journal, September 2017

    • Rungthanaphatsophon, Pokpong; Bathelier, Adrien; Castro, Ludovic
    • Angewandte Chemie International Edition, Vol. 56, Issue 42
    • DOI: 10.1002/anie.201706496

    A Theoretical Study of Uranium(IV) Bis-Methyl Complexes: Towards the Predictive Formation of a Transient Uranium(IV) Carbene Complex
    journal, April 2010

    • Yahia, Ahmed; Castro, Ludovic; Maron, Laurent
    • Chemistry - A European Journal, Vol. 16, Issue 19
    • DOI: 10.1002/chem.201000022

    The Nature of the UC Double Bond: Pushing the Stability of High-Oxidation-State Uranium Carbenes to the Limit
    journal, April 2013

    • Cooper, Oliver J.; Mills, David P.; McMaster, Jonathan
    • Chemistry - A European Journal, Vol. 19, Issue 22
    • DOI: 10.1002/chem.201300071

    Inverted sandwich arene complexes of uranium
    journal, June 2015


    Uranium carbene compounds
    journal, April 2013


    Evidence for the Existence of Group 3 Terminal Methylidene Complexes
    journal, July 2016


    Synthesis, Thermochemistry, Bonding, and 13 C NMR Chemical Shift Analysis of a Phosphorano-Stabilized Carbene of Thorium
    journal, April 2017


    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

    Magnetic Susceptibility of Uranium Complexes
    journal, August 2014

    • Kindra, Douglas R.; Evans, William J.
    • Chemical Reviews, Vol. 114, Issue 18
    • DOI: 10.1021/cr500242w

    Multiconfigurational Second-Order Perturbation Theory Restricted Active Space (RASPT2) Method for Electronic Excited States: A Benchmark Study
    journal, December 2010

    • Sauri, Vicenta; Serrano-Andrés, Luis; Shahi, Abdul Rehaman Moughal
    • Journal of Chemical Theory and Computation, Vol. 7, Issue 1
    • DOI: 10.1021/ct100478d

    Synthesis and Characterization of N-Heterocyclic Carbene Complexes of Uranium(III)
    journal, February 2004

    • Nakai, Hidetaka; Hu, Xile; Zakharov, Lev N.
    • Inorganic Chemistry, Vol. 43, Issue 3
    • DOI: 10.1021/ic035142j

    Formation and Characterization of the Uranium Methylidene Complexes CH 2 UHX (X = F, Cl, and Br)
    journal, February 2006

    • Lyon, Jonathan T.; Andrews, Lester
    • Inorganic Chemistry, Vol. 45, Issue 4
    • DOI: 10.1021/ic051785i

    Infrared Spectrum and Bonding in Uranium Methylidene Dihydride, CH 2 UH 2
    journal, June 2007

    • Lyon, Jonathan T.; Andrews, Lester; Malmqvist, Per-Åke
    • Inorganic Chemistry, Vol. 46, Issue 12
    • DOI: 10.1021/ic062407w

    Oxidation State Delineation via U L III -Edge XANES in a Series of Isostructural Uranium Coordination Complexes
    journal, April 2012

    • Kosog, Boris; La Pierre, Henry S.; Denecke, Melissa A.
    • Inorganic Chemistry, Vol. 51, Issue 14
    • DOI: 10.1021/ic3011234

    Infrared Spectra and Electronic Structures of Agostic Uranium Methylidene Molecules
    journal, March 2008

    • Lyon, Jonathan T.; Andrews, Lester; Hu, Han-Shi
    • Inorganic Chemistry, Vol. 47, Issue 5
    • DOI: 10.1021/ic701786h

    Comparative Study of f-Element Electronic Structure across a Series of Multimetallic Actinide and Lanthanoid-Actinide Complexes Possessing Redox-Active Bridging Ligands
    journal, February 2010

    • Schelter, Eric J.; Wu, Ruilian; Veauthier, Jacqueline M.
    • Inorganic Chemistry, Vol. 49, Issue 4
    • DOI: 10.1021/ic9024475

    Synthesis and Single Crystal X-ray Diffraction Study on the First Isolable Carbonyl Complex of an Actinide, (C5Me4H)3U(CO)
    journal, March 1995

    • Parry, Julian; Carmona, Ernesto; Coles, Simon
    • Journal of the American Chemical Society, Vol. 117, Issue 9
    • DOI: 10.1021/ja00114a030

    Preparation of the first molecular carbon monoxide complex of uranium, (Me3SiC5H4)3UCO
    journal, January 1986

    • Brennan, John G.; Andersen, Richard A.; Robbins, John L.
    • Journal of the American Chemical Society, Vol. 108, Issue 2
    • DOI: 10.1021/ja00262a046

    Supported organoactinides. Surface chemistry and catalytic properties of alumina-bound cyclopentadienyl and pentamethylcyclopentadienyl thorium and uranium hydrocarbyls and hydrides
    journal, February 1985

    • He, Ming Yuan; Xiong, Guoxing; Toscano, Paul J.
    • Journal of the American Chemical Society, Vol. 107, Issue 3
    • DOI: 10.1021/ja00289a016

    Uranium carbon multiple-bond chemistry. 3. Insertion of acetonitrile and the formation of a uranium nitrogen multiple bond
    journal, March 1984

    • Cramer, Roger E.; Panchanatheswaran, K.; Gilje, John W.
    • Journal of the American Chemical Society, Vol. 106, Issue 6
    • DOI: 10.1021/ja00318a059

    Uranium-carbon multiple-bond chemistry. 4. Addition of coordinated carbon monoxide across a uranium-carbon multiple bond
    journal, November 1984

    • Cramer, Roger E.; Higa, Kelvin T.; Gilje, John W.
    • Journal of the American Chemical Society, Vol. 106, Issue 23
    • DOI: 10.1021/ja00335a065

    Description of conjugation and hyperconjugation in terms of electron distributions
    journal, July 1983

    • Bader, R. F. W.; Slee, T. S.; Cremer, D.
    • Journal of the American Chemical Society, Vol. 105, Issue 15
    • DOI: 10.1021/ja00353a035

    Uranium-carbon multiple bond chemistry. 2. Coupling of bridging and terminal carbonyls in the formation of an iron .eta.1:.eta.3-allyl complex
    journal, October 1983

    • Cramer, Roger E.; Higa, Kelvin T.; Pruskin, Steven L.
    • Journal of the American Chemical Society, Vol. 105, Issue 22
    • DOI: 10.1021/ja00360a052

    A uranium-carbon multiple bond. Crystal and molecular structure of (.eta.5-C5H5)3UCHP(CH3)2(C6H5)
    journal, June 1981

    • Cramer, Roger E.; Maynard, Richard B.; Paw, Josephine C.
    • Journal of the American Chemical Society, Vol. 103, Issue 12
    • DOI: 10.1021/ja00402a065

    Comparative Reactivity of Sterically Crowded nf 3 (C 5 Me 5 ) 3 Nd and (C 5 Me 5 ) 3 U Complexes with CO:  Formation of a Nonclassical Carbonium Ion versus an f Element Metal Carbonyl Complex
    journal, November 2003

    • Evans, William J.; Kozimor, Stosh A.; Nyce, Gregory W.
    • Journal of the American Chemical Society, Vol. 125, Issue 45
    • DOI: 10.1021/ja036631l

    A Monometallic f Element Complex of Dinitrogen:  (C 5 Me 5 ) 3 U(η 1 -N 2 )
    journal, November 2003

    • Evans, William J.; Kozimor, Stosh A.; Ziller, Joseph W.
    • Journal of the American Chemical Society, Vol. 125, Issue 47
    • DOI: 10.1021/ja037647e

    Structure, Reactivity, and Density Functional Theory Analysis of the Six-Electron Reductant, [(C 5 Me 5 ) 2 U] 2- η 66 -C 6 H 6 ), Synthesized via a New Mode of (C 5 Me 5 ) 3 M Reactivity
    journal, November 2004

    • Evans, William J.; Kozimor, Stosh A.; Ziller, Joseph W.
    • Journal of the American Chemical Society, Vol. 126, Issue 44
    • DOI: 10.1021/ja0463886

    Synthesis of a Phosphorano-Stabilized U(IV)-Carbene via One-Electron Oxidation of a U(III)-Ylide Adduct
    journal, May 2011

    • Fortier, Skye; Walensky, Justin R.; Wu, Guang
    • Journal of the American Chemical Society, Vol. 133, Issue 18
    • DOI: 10.1021/ja2001133

    Exploring the Uranyl Organometallic Chemistry: From Single to Double Uranium−Carbon Bonds
    journal, April 2011

    • Tourneux, Jean-Christophe; Berthet, Jean-Claude; Cantat, Thibault
    • Journal of the American Chemical Society, Vol. 133, Issue 16
    • DOI: 10.1021/ja201276h

    Synthesis, Structure, and Magnetism of an f Element Nitrosyl Complex, (C 5 Me 4 H) 3 UNO
    journal, December 2011

    • Siladke, Nathan A.; Meihaus, Katie R.; Ziller, Joseph W.
    • Journal of the American Chemical Society, Vol. 134, Issue 2
    • DOI: 10.1021/ja2096128

    Probing the 5f Orbital Contribution to the Bonding in a U(V) Ketimide Complex
    journal, February 2012

    • Seaman, Lani A.; Wu, Guang; Edelstein, Norman
    • Journal of the American Chemical Society, Vol. 134, Issue 10
    • DOI: 10.1021/ja211875s

    Tetrahalide Complexes of the [U(NR) 2 ] 2+ Ion: Synthesis, Theory, and Chlorine K-Edge X-ray Absorption Spectroscopy
    journal, January 2013

    • Spencer, Liam P.; Yang, Ping; Minasian, Stefan G.
    • Journal of the American Chemical Society, Vol. 135, Issue 6
    • DOI: 10.1021/ja310575j

    Quantifying the σ and π Interactions between U(V) f Orbitals and Halide, Alkyl, Alkoxide, Amide and Ketimide Ligands
    journal, July 2013

    • Lukens, Wayne W.; Edelstein, Norman M.; Magnani, Nicola
    • Journal of the American Chemical Society, Vol. 135, Issue 29
    • DOI: 10.1021/ja403815h

    Identification of the +2 Oxidation State for Uranium in a Crystalline Molecular Complex, [K(2.2.2-Cryptand)][(C 5 H 4 SiMe 3 ) 3 U]
    journal, August 2013

    • MacDonald, Matthew R.; Fieser, Megan E.; Bates, Jefferson E.
    • Journal of the American Chemical Society, Vol. 135, Issue 36
    • DOI: 10.1021/ja406791t

    Investigation of the Electronic Ground States for a Reduced Pyridine(diimine) Uranium Series: Evidence for a Ligand Tetraanion Stabilized by a Uranium Dimer
    journal, April 2015

    • Anderson, Nickolas H.; Odoh, Samuel O.; Williams, Ursula J.
    • Journal of the American Chemical Society, Vol. 137, Issue 14
    • DOI: 10.1021/ja511867a

    The UC Double Bond: Synthesis and Study of Uranium Nucleophilic Carbene Complexes
    journal, January 2009

    • Cantat, Thibault; Arliguie, Thérèse; Noël, Anne
    • Journal of the American Chemical Society, Vol. 131, Issue 3
    • DOI: 10.1021/ja807282s

    Trends in Covalency for d- and f-Element Metallocene Dichlorides Identified Using Chlorine K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory
    journal, September 2009

    • Kozimor, Stosh A.; Yang, Ping; Batista, Enrique R.
    • Journal of the American Chemical Society, Vol. 131, Issue 34
    • DOI: 10.1021/ja9015759

    Arene-Bridged Diuranium Complexes:  Inverted Sandwiches Supported by δ Backbonding
    journal, June 2000

    • Diaconescu, Paula L.; Arnold, Polly L.; Baker, Thomas A.
    • Journal of the American Chemical Society, Vol. 122, Issue 25
    • DOI: 10.1021/ja994484e

    Synthesis and Structure of Nitride-Bridged Uranium(III) Complexes
    journal, February 2016

    • Chatelain, Lucile; Scopelliti, Rosario; Mazzanti, Marinella
    • Journal of the American Chemical Society, Vol. 138, Issue 6
    • DOI: 10.1021/jacs.5b12620

    Agostic Interaction in the Methylidene Metal Dihydride Complexes H 2 MCH 2 (M = Y, Zr, Nb, Mo, Ru, Th, or U)
    journal, July 2007

    • Roos, Björn O.; Lindh, Roland; Cho, Han-Gook
    • The Journal of Physical Chemistry A, Vol. 111, Issue 28
    • DOI: 10.1021/jp071914b

    Dinuclear Trivalent and Mixed-Valence Uranium [(−CH 2 −) 5 ] 4 -calix[4]tetrapyrrole Complexes with Short Intermetallic Distances
    journal, December 2001

    • Korobkov, Ilia; Gambarotta, Sandro; Yap, Glenn P. A.
    • Organometallics, Vol. 20, Issue 25
    • DOI: 10.1021/om010510h

    Uranium(IV) Nucleophilic Carbene Complexes
    journal, June 2011

    • Tourneux, Jean-Christophe; Berthet, Jean-Claude; Cantat, Thibault
    • Organometallics, Vol. 30, Issue 11
    • DOI: 10.1021/om200006g

    Investigations of the Electronic Structure of Arene-Bridged Diuranium Complexes
    journal, January 2013

    • Vlaisavljevich, Bess; Diaconescu, Paula L.; Lukens, Wayne L.
    • Organometallics, Vol. 32, Issue 5
    • DOI: 10.1021/om3010367

    A delocalized arene-bridged diuranium single-molecule magnet
    journal, April 2011

    • Mills, David P.; Moro, Fabrizio; McMaster, Jonathan
    • Nature Chemistry, Vol. 3, Issue 6
    • DOI: 10.1038/nchem.1028

    Actinide covalency measured by pulsed electron paramagnetic resonance spectroscopy
    journal, December 2016

    • Formanuik, Alasdair; Ariciu, Ana-Maria; Ortu, Fabrizio
    • Nature Chemistry, Vol. 9, Issue 6
    • DOI: 10.1038/nchem.2692

    Incipient class II mixed valency in a plutonium solid-state compound
    journal, May 2017

    • Cary, Samantha K.; Galley, Shane S.; Marsh, Matthew L.
    • Nature Chemistry, Vol. 9, Issue 9
    • DOI: 10.1038/nchem.2777

    The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes
    journal, February 2017

    • Gregson, Matthew; Lu, Erli; Mills, David P.
    • Nature Communications, Vol. 8, Issue 1
    • DOI: 10.1038/ncomms14137

    Double dative bond between divalent carbon(0) and uranium
    journal, November 2018


    Small molecule activation at uranium coordination complexes: control of reactivity via molecular architecture
    journal, January 2006

    • Castro-Rodríguez, Ingrid; Meyer, Karsten
    • Chemical Communications, Issue 13
    • DOI: 10.1039/b513755c

    Easy access to uranium nucleophilic carbene complexes
    journal, January 2010

    • Tourneux, Jean-Christophe; Berthet, Jean-Claude; Thuéry, Pierre
    • Dalton Transactions, Vol. 39, Issue 10
    • DOI: 10.1039/b926718m

    Early metal bis(phosphorus-stabilised)carbene chemistry
    journal, January 2011

    • Liddle, Stephen T.; Mills, David P.; Wooles, Ashley J.
    • Chemical Society Reviews, Vol. 40, Issue 5
    • DOI: 10.1039/c0cs00135j

    Synthesis and structure of [U{C(PPh2NMes)2}2] (Mes = 2,4,6-Me3C6H2): A homoleptic uranium bis(carbene) complex with two formal UC double bonds
    journal, January 2010

    • Cooper, Oliver J.; McMaster, Jonathan; Lewis, William
    • Dalton Transactions, Vol. 39, Issue 21
    • DOI: 10.1039/c0dt00152j

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


    A mixed-valence uranium(III/IV) bimetallic; structure, magnetism and reactivity
    journal, January 1996

    • Roussel, Paul; Hitchcock, Peter B.; Tinker, Nigel
    • Chemical Communications, Issue 17
    • DOI: 10.1039/cc9960002053

    Molecular Octa-Uranium Rings with Alternating Nitride and Azide Bridges
    journal, September 2005


    Reactions of Actinide Metal Atoms with Ethane: Computation and Observation of New Th and U Ethylidene Dihydride, Metallacyclopropane Dihydride, and Vinyl Metal Trihydride Complexes
    journal, July 2008

    • Cho, Han-Gook; Lyon, Jonathan T.; Andrews, Lester
    • The Journal of Physical Chemistry A, Vol. 112, Issue 30
    • DOI: 10.1021/jp801692s

    Rare-Earth- and Uranium-Mesoionic Carbenes: A New Class of f-Block Carbene Complex Derived from an N-Heterocyclic Olefin
    journal, August 2017

    • Seed, John A.; Gregson, Matthew; Tuna, Floriana
    • Angewandte Chemie International Edition, Vol. 56, Issue 38
    • DOI: 10.1002/anie.201706546

    The role of the 5f valence orbitals of early actinides in chemical bonding
    journal, July 2017

    • Vitova, T.; Pidchenko, I.; Fellhauer, D.
    • Nature Communications, Vol. 8, Issue 1
    • DOI: 10.1038/ncomms16053

    Covalent Uranium Carbene Chemistry
    journal, March 2015


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