Homoleptic Aryl Complexes of Uranium (IV)
Abstract
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.
- Authors:
-
[1];
[2];
[1];
[2];
[1]
- Univ. of Rochester, NY (United States)
- State Univ. of New York (SUNY), Buffalo, NY (United States)
- Publication Date:
- Research Org.:
- State Univ. of New York (SUNY), Albany, NY (United States); Univ. of Rochester, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1610533
- Alternate Identifier(s):
- OSTI ID: 1529026
- Grant/Contract Number:
- SC0001136; SC0016002
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 58; Journal Issue: 30; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry
Citation Formats
Wolford, Nikki J., Sergentu, Dumitru‐Claudiu, Brennessel, William W., Autschbach, Jochen, and Neidig, Michael L. Homoleptic Aryl Complexes of Uranium (IV). United States: N. p., 2019.
Web. doi:10.1002/anie.201905423.
Wolford, Nikki J., Sergentu, Dumitru‐Claudiu, Brennessel, William W., Autschbach, Jochen, & Neidig, Michael L. Homoleptic Aryl Complexes of Uranium (IV). United States. https://doi.org/10.1002/anie.201905423
Wolford, Nikki J., Sergentu, Dumitru‐Claudiu, Brennessel, William W., Autschbach, Jochen, and Neidig, Michael L. Mon .
"Homoleptic Aryl Complexes of Uranium (IV)". United States. https://doi.org/10.1002/anie.201905423. https://www.osti.gov/servlets/purl/1610533.
@article{osti_1610533,
title = {Homoleptic Aryl Complexes of Uranium (IV)},
author = {Wolford, Nikki J. and Sergentu, Dumitru‐Claudiu and Brennessel, William W. and Autschbach, Jochen and Neidig, Michael L.},
abstractNote = {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.},
doi = {10.1002/anie.201905423},
journal = {Angewandte Chemie (International Edition)},
number = 30,
volume = 58,
place = {United States},
year = {Mon Jun 24 00:00:00 EDT 2019},
month = {Mon Jun 24 00:00:00 EDT 2019}
}
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Works referenced in this record:
New Benzylpotassium Reagents and Their Utility for the Synthesis of Homoleptic Uranium(IV) Benzyl Derivatives
journal, May 2015
- Johnson, Sara A.; Kiernicki, John J.; Fanwick, Phillip E.
- Organometallics, Vol. 34, Issue 12
Homoleptic Organometallic Anions of Ti, Zr, Hf, and Nb
journal, March 2011
- El-Kurdi, Said; Seppelt, Konrad
- Chemistry - A European Journal, Vol. 17, Issue 14
Homoleptic Uranium(IV) Alkyl Complexes: Synthesis and Characterization
journal, October 2009
- Fortier, Skye; Melot, Brent C.; Wu, Guang
- Journal of the American Chemical Society, Vol. 131, Issue 42
Observations on the thermal decomposition of some uranium(IV) tetraalkyls
journal, January 1974
- Marks, Tobin J.; Seyam, Afif M.
- Journal of Organometallic Chemistry, Vol. 67, Issue 1
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
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
journal, April 2011
- Monreal, Marisa J.; Thomson, Robert K.; Cantat, Thibault
- Organometallics, Vol. 30, Issue 7
Magnetic circular dichroism of UCl 6 − in the ligand-to-metal charge-transfer spectral region
journal, January 2017
- Gendron, Frédéric; Fleischauer, Valerie E.; Duignan, Thomas J.
- Physical Chemistry Chemical Physics, Vol. 19, Issue 26
High-Valent Uranium Alkyls: Evidence for the Formation of U VI (CH 2 SiMe 3 ) 6
journal, August 2011
- Fortier, Skye; Walensky, Justin R.; Wu, Guang
- Journal of the American Chemical Society, Vol. 133, Issue 30
A Homoleptic Uranium(III) Tris(aryl) Complex
journal, December 2016
- Boreen, Michael A.; Parker, Bernard F.; Lohrey, Trevor D.
- Journal of the American Chemical Society, Vol. 138, Issue 49
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
journal, June 2008
- Fortier, Skye; Wu, Guang; Hayton, Trevor W.
- Inorganic Chemistry, Vol. 47, Issue 11
First example of a neutral homoleptic uranium alkyl. Synthesis, properties, and structure of U[CH(SiMe3)2]3
journal, March 1989
- Van der Sluys, William G.; Burns, Carol J.; Sattelberger, Alfred P.
- Organometallics, Vol. 8, Issue 3
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
journal, January 2018
- Carpenter, Stephanie H.; Baker, Tessa M.; Muñoz, Salvador B.
- Chemical Science, Vol. 9, Issue 41
Carbon–Carbon Reductive Elimination from Homoleptic Uranium(IV) Alkyls Induced by Redox-Active Ligands
journal, April 2012
- Kraft, Steven J.; Fanwick, Phillip E.; Bart, Suzanne C.
- Journal of the American Chemical Society, Vol. 134, Issue 14
Organic Compounds of Uranium. I. 1,3-Dicarbonyl Chelates
journal, June 1956
- Gilman, H.; Jones, R. G.; Bindschadler, E.
- Journal of the American Chemical Society, Vol. 78, Issue 12
Lithium alkyl anions of uranium(IV) and uranium(V). Addition compounds of uranium(VI) hexaisopropoxide with lithium, magnesium, and aluminium alkyls
journal, January 1977
- Sigurdson, Elin R.; Wilkinson, Geoffrey
- Journal of the Chemical Society, Dalton Transactions, Issue 8
Some octahedral complexes of uranium(IV)
journal, January 1966
- Day, J. P.; Venanzi, L. M.
- Journal of the Chemical Society A: Inorganic, Physical, Theoretical
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
journal, January 2011
- Seaman, Lani A.; Fortier, Skye; Wu, Guang
- Inorganic Chemistry, Vol. 50, Issue 2
Synthesis, structure and bonding of hexaphenyl thorium( iv ): observation of a non-octahedral structure
journal, January 2016
- Pedrick, Elizabeth A.; Hrobárik, Peter; Seaman, Lani A.
- Chemical Communications, Vol. 52, Issue 4