Homoleptic Aryl Complexes of Uranium (IV)

Wolford, Nikki J.; Sergentu, Dumitru‐Claudiu; Brennessel, William W.; Autschbach, Jochen; Neidig, Michael L.

doi:10.1002/ange.201905423

Title: Homoleptic Aryl Complexes of Uranium (IV)

Journal Article · 24 June 2019 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.201905423 · OSTI ID:1560219

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Department of Chemistry University of Rochester, B31 Hutchison Hall 120 Trustee Road Rochester NY 14627 USA
Department of Chemistry University at Buffalo State University of New York 312 Natural Sciences Complex Buffalo NY 14260 USA

Abstract The synthesis and characterization of sterically unencumbered homoleptic organouranium aryl complexes containing U−C σ‐bonds has been of interest to the chemical community for over 70 years. Reported herein are the first structurally characterized, sterically unencumbered homoleptic uranium (IV) aryl‐ate species of the form [U(Ar) ₆ ] ²⁻ (Ar=Ph, p ‐tolyl, p ‐Cl‐Ph). Magnetic circular dichroism (MCD) spectroscopy and computational studies provide insight into electronic structure and bonding interactions in the U−C σ‐bond across this series of complexes. Overall, these studies solve a decades‐long challenge in synthetic uranium chemistry, enabling new insight into electronic structure and bonding in organouranium complexes.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0001136; SC0016002

OSTI ID:: 1560219

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 30 Vol. 131; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (18)

Homoleptic Organometallic Anions of Ti, Zr, Hf, and Nb El-Kurdi, Said; Seppelt, Konrad Chemistry - A European Journal, Vol. 17, Issue 14 https://doi.org/10.1002/chem.201003323	journal	March 2011
Observations on the thermal decomposition of some uranium(IV) tetraalkyls Marks, Tobin J.; Seyam, Afif M. Journal of Organometallic Chemistry, Vol. 67, Issue 1 https://doi.org/10.1016/S0022-328X(00)93684-2	journal	January 1974
New Benzylpotassium Reagents and Their Utility for the Synthesis of Homoleptic Uranium(IV) Benzyl Derivatives Johnson, Sara A.; Kiernicki, John J.; Fanwick, Phillip E. Organometallics, Vol. 34, Issue 12 https://doi.org/10.1021/acs.organomet.5b00212	journal	May 2015
Comparison of the Redox Chemistry of Primary and Secondary Amides of U(IV): Isolation of a U(VI) Bis(imido) Complex or a Homoleptic U(VI) Amido Complex Seaman, Lani A.; Fortier, Skye; Wu, Guang Inorganic Chemistry, Vol. 50, Issue 2 https://doi.org/10.1021/ic101847b	journal	January 2011
Synthesis and Characterization of Three Homoleptic Alkoxides of Uranium: [Li(THF)] ₂ [U ^IV (O ^t Bu) ₆ ], [Li(Et ₂ O)][U ^V (O ^t Bu) ₆ ], and U ^VI (O ^t Bu) ₆ Fortier, Skye; Wu, Guang; Hayton, Trevor W. Inorganic Chemistry, Vol. 47, Issue 11 https://doi.org/10.1021/ic800067k	journal	June 2008
Organic Compounds of Uranium. I. 1,3-Dicarbonyl Chelates Gilman, H.; Jones, R. G.; Bindschadler, E. Journal of the American Chemical Society, Vol. 78, Issue 12 https://doi.org/10.1021/ja01593a038	journal	June 1956
High-Valent Uranium Alkyls: Evidence for the Formation of U ^VI (CH ₂ SiMe ₃ ) ₆ Fortier, Skye; Walensky, Justin R.; Wu, Guang Journal of the American Chemical Society, Vol. 133, Issue 30 https://doi.org/10.1021/ja204151v	journal	August 2011
Carbon–Carbon Reductive Elimination from Homoleptic Uranium(IV) Alkyls Induced by Redox-Active Ligands Kraft, Steven J.; Fanwick, Phillip E.; Bart, Suzanne C. Journal of the American Chemical Society, Vol. 134, Issue 14 https://doi.org/10.1021/ja209524u	journal	April 2012
Probing the 5f Orbital Contribution to the Bonding in a U(V) Ketimide Complex Seaman, Lani A.; Wu, Guang; Edelstein, Norman Journal of the American Chemical Society, Vol. 134, Issue 10 https://doi.org/10.1021/ja211875s	journal	February 2012
Homoleptic Uranium(IV) Alkyl Complexes: Synthesis and Characterization Fortier, Skye; Melot, Brent C.; Wu, Guang Journal of the American Chemical Society, Vol. 131, Issue 42 https://doi.org/10.1021/ja906516e	journal	October 2009
A Homoleptic Uranium(III) Tris(aryl) Complex Boreen, Michael A.; Parker, Bernard F.; Lohrey, Trevor D. Journal of the American Chemical Society, Vol. 138, Issue 49 https://doi.org/10.1021/jacs.6b11182	journal	December 2016
First example of a neutral homoleptic uranium alkyl. Synthesis, properties, and structure of U[CH(SiMe3)2]3 Van der Sluys, William G.; Burns, Carol J.; Sattelberger, Alfred P. Organometallics, Vol. 8, Issue 3 https://doi.org/10.1021/om00105a051	journal	March 1989
UI ₄ (1,4-dioxane) ₂ , [UCl ₄ (1,4-dioxane)] ₂ , and UI ₃ (1,4-dioxane) _1.5 : Stable and Versatile Starting Materials for Low- and High-Valent Uranium Chemistry Monreal, Marisa J.; Thomson, Robert K.; Cantat, Thibault Organometallics, Vol. 30, Issue 7 https://doi.org/10.1021/om200093q	journal	April 2011
Synthesis, structure and bonding of hexaphenyl thorium( iv ): observation of a non-octahedral structure Pedrick, Elizabeth A.; Hrobárik, Peter; Seaman, Lani A. Chemical Communications, Vol. 52, Issue 4 https://doi.org/10.1039/C5CC08265J	journal	January 2016
Magnetic circular dichroism of UCl ₆ ⁻ in the ligand-to-metal charge-transfer spectral region Gendron, Frédéric; Fleischauer, Valerie E.; Duignan, Thomas J. Physical Chemistry Chemical Physics, Vol. 19, Issue 26 https://doi.org/10.1039/C7CP02572F	journal	January 2017
Multinuclear iron–phenyl species in reactions of simple iron salts with PhMgBr: identification of Fe ₄ (μ-Ph) ₆ (THF) ₄ as a key reactive species for cross-coupling catalysis Carpenter, Stephanie H.; Baker, Tessa M.; Muñoz, Salvador B. Chemical Science, Vol. 9, Issue 41 https://doi.org/10.1039/C8SC02915F	journal	January 2018
Lithium alkyl anions of uranium(IV) and uranium(V). Addition compounds of uranium(VI) hexaisopropoxide with lithium, magnesium, and aluminium alkyls Sigurdson, Elin R.; Wilkinson, Geoffrey Journal of the Chemical Society, Dalton Transactions, Issue 8 https://doi.org/10.1039/dt9770000812	journal	January 1977
Some octahedral complexes of uranium(IV) Day, J. P.; Venanzi, L. M. Journal of the Chemical Society A: Inorganic, Physical, Theoretical https://doi.org/10.1039/j19660000197	journal	January 1966

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