Ligand effects on electronic structure and bonding in U(iii) coordination complexes: a combined MCD, EPR and computational study
Abstract
The trivalent oxidation state of uranium has been shown to undergo unique reactivity, from its ability to activate a variety of small molecules to its role in the catalytic reduction of ethene to ethane amongst others. Central to this unique reactivity and ability to rationally design ligands for isotope separation is the underlying uranium electronic structure. While electronic structure studies of U(IV), U(V), and U(VI) have been extensive, by comparison, analogous studies of more reduced oxidation states such as U(III) remains underdeveloped. Herein we report a combined MCD and EPR spectroscopic approach along with density functional theory and multireference wavefunction calculations to elucidate the effects of ligand perturbation in three uranium(III) Tp* complexes. Overall, the experimental and computational insight suggests that the change in ligand environment across this series of U(III) complexes resulted in only minor perturbations in the uranium electronic structure. This combined approach was also used to redefine the electronic ground state of a U(III) complex with a redox non-innocent Bipy- ligand. Overall, these studies demonstrate the efficacy of the combined experimental and theoretical approach towards evaluating electronic structure and bonding in U(III) complexes and provide important insight into the challenges in altering ligand environments to modify bondingmore »
- Authors:
-
[1];
[2];
[3];
[2];
[1]
- Univ. of Rochester, NY (United States)
- Univ. at Buffalo, NY (United States)
- Purdue Univ., West Lafayette, IN (United States)
- Publication Date:
- Research Org.:
- Univ. at Buffalo, NY (United States); Univ. of Rochester, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1850721
- Alternate Identifier(s):
- OSTI ID: 1669185
- Grant/Contract Number:
- SC0001136; SC0016002; SC0016568
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Dalton Transactions
- Additional Journal Information:
- Journal Volume: 49; Journal Issue: 41; 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
Wolford, Nikki J., Yu, Xiaojuan, Bart, Suzanne C., Autschbach, Jochen, and Neidig, Michael L. Ligand effects on electronic structure and bonding in U(iii) coordination complexes: a combined MCD, EPR and computational study. United States: N. p., 2020.
Web. doi:10.1039/d0dt02929g.
Wolford, Nikki J., Yu, Xiaojuan, Bart, Suzanne C., Autschbach, Jochen, & Neidig, Michael L. Ligand effects on electronic structure and bonding in U(iii) coordination complexes: a combined MCD, EPR and computational study. United States. https://doi.org/10.1039/d0dt02929g
Wolford, Nikki J., Yu, Xiaojuan, Bart, Suzanne C., Autschbach, Jochen, and Neidig, Michael L. Thu .
"Ligand effects on electronic structure and bonding in U(iii) coordination complexes: a combined MCD, EPR and computational study". United States. https://doi.org/10.1039/d0dt02929g. https://www.osti.gov/servlets/purl/1850721.
@article{osti_1850721,
title = {Ligand effects on electronic structure and bonding in U(iii) coordination complexes: a combined MCD, EPR and computational study},
author = {Wolford, Nikki J. and Yu, Xiaojuan and Bart, Suzanne C. and Autschbach, Jochen and Neidig, Michael L.},
abstractNote = {The trivalent oxidation state of uranium has been shown to undergo unique reactivity, from its ability to activate a variety of small molecules to its role in the catalytic reduction of ethene to ethane amongst others. Central to this unique reactivity and ability to rationally design ligands for isotope separation is the underlying uranium electronic structure. While electronic structure studies of U(IV), U(V), and U(VI) have been extensive, by comparison, analogous studies of more reduced oxidation states such as U(III) remains underdeveloped. Herein we report a combined MCD and EPR spectroscopic approach along with density functional theory and multireference wavefunction calculations to elucidate the effects of ligand perturbation in three uranium(III) Tp* complexes. Overall, the experimental and computational insight suggests that the change in ligand environment across this series of U(III) complexes resulted in only minor perturbations in the uranium electronic structure. This combined approach was also used to redefine the electronic ground state of a U(III) complex with a redox non-innocent Bipy- ligand. Overall, these studies demonstrate the efficacy of the combined experimental and theoretical approach towards evaluating electronic structure and bonding in U(III) complexes and provide important insight into the challenges in altering ligand environments to modify bonding and reactivity in uranium coordination chemistry.},
doi = {10.1039/d0dt02929g},
journal = {Dalton Transactions},
number = 41,
volume = 49,
place = {United States},
year = {Thu Sep 24 00:00:00 EDT 2020},
month = {Thu Sep 24 00:00:00 EDT 2020}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Magnetic Properties and Electronic Structure of Neptunyl(VI) Complexes: Wavefunctions, Orbitals, and Crystal-Field Models
journal, May 2014
- Gendron, Frédéric; Páez-Hernández, Dayán; Notter, François-Paul
- Chemistry - A European Journal, Vol. 20, Issue 26
An N -Tethered Uranium(III) Arene Complex and the Synthesis of an Unsupported U–Fe Bond
journal, July 2017
- Fortier, Skye; Aguilar-Calderón, J. Rolando; Vlaisavljevich, Bess
- Organometallics, Vol. 36, Issue 23
The roles of 4f- and 5f-orbitals in bonding: a magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study
journal, January 2016
- Lukens, W. W.; Speldrich, M.; Yang, P.
- Dalton Transactions, Vol. 45, Issue 28
Spectroscopic Determination of the Electronic Structure of a Uranium Single-Ion Magnet
journal, January 2019
- Coutinho, Joana T.; Perfetti, Mauro; Baldoví, José J.
- Chemistry - A European Journal, Vol. 25, Issue 7
Uranium (III) Scorpionates: Synthesis and Structure of [(Tp Me 2 ) 2 U{N(C 6 H 5 ) 2 }] and [(Tp Me 2 ) 2 U{N(SiMe 3 ) 2 }]
journal, October 2004
- Antunes, Maria Augusta; Ferrence, Gregory M.; Domingos, Ângela
- Inorganic Chemistry, Vol. 43, Issue 21
Werner-Type Complexes of Uranium(III) and (IV)
journal, January 2020
- Riedhammer, Judith; Aguilar-Calderón, J. Rolando; Miehlich, Matthias
- Inorganic Chemistry, Vol. 59, Issue 4
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
Dispersion Forces Drive the Formation of Uranium–Alkane Adducts
journal, December 2019
- Jung, Julie; Löffler, Sascha T.; Langmann, Jan
- Journal of the American Chemical Society, Vol. 142, Issue 4
Influence of Pyrazolate vs N -Heterocyclic Carbene Ligands on the Slow Magnetic Relaxation of Homoleptic Trischelate Lanthanide(III) and Uranium(III) Complexes
journal, April 2014
- Meihaus, Katie R.; Minasian, Stefan G.; Lukens, Wayne W.
- Journal of the American Chemical Society, Vol. 136, Issue 16
Absorption spectra analysis of hydrated uranium(III) complex chlorides
journal, November 2000
- Karbowiak, M.; Gajek, Z.; Drożdżyński, J.
- Chemical Physics, Vol. 261, Issue 3
Small-Molecule Activation at Uranium(III)
journal, April 2013
- Gardner, Benedict M.; Liddle, Stephen T.
- European Journal of Inorganic Chemistry, Vol. 2013, Issue 22-23
Modern quantum chemistry with [Open]Molcas
journal, June 2020
- Aquilante, Francesco; Autschbach, Jochen; Baiardi, Alberto
- The Journal of Chemical Physics, Vol. 152, Issue 21
OpenMolcas: From Source Code to Insight
journal, September 2019
- Fdez. Galván, Ignacio; Vacher, Morgane; Alavi, Ali
- Journal of Chemical Theory and Computation, Vol. 15, Issue 11
A Uranium Tri-Rhenium Triple Inverse Sandwich Compound
journal, March 2019
- Boreen, Michael A.; Lohrey, Trevor D.; Rao, Guodong
- Journal of the American Chemical Society, Vol. 141, Issue 13
Uranium( iii ) complexes supported by hydrobis(mercaptoimidazolyl)borates: synthesis and oxidation chemistry
journal, January 2018
- Maria, Leonor; Santos, Isabel C.; Santos, Isabel
- Dalton Transactions, Vol. 47, Issue 31
Functionalization of Carbon Dioxide and Carbon Disulfide Using a Stable Uranium(III) Alkyl Complex
journal, April 2011
- Matson, Ellen M.; Forrest, William P.; Fanwick, Phillip E.
- Journal of the American Chemical Society, Vol. 133, Issue 13
Bipyridine: The Most Widely Used Ligand. A Review of Molecules Comprising at Least Two 2,2‘-Bipyridine Units
journal, October 2000
- Kaes, Christian; Katz, Alexander; Hosseini, Mir Wais
- Chemical Reviews, Vol. 100, Issue 10
The Renaissance of Non-Aqueous Uranium Chemistry
journal, June 2015
- Liddle, Stephen T.
- Angewandte Chemie International Edition, Vol. 54, Issue 30
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
Multicoordinate ligands for actinide/lanthanide separations
journal, January 2007
- Dam, Henk H.; Reinhoudt, David N.; Verboom, Willem
- Chem. Soc. Rev., Vol. 36, Issue 2
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
Synthesis and Structure of Bis[hydrotris(3,5-dimethylpyrazolyl)borato]iodouranium(III), U[HB(3,5-Me2pz)3]2I: Unprecedented Side-On Interaction Involving a Hydrotris(pyrazolyl)borate Ligand
journal, September 1994
- Sun, Yimin; McDonald, Robert; Takats, Josef
- Inorganic Chemistry, Vol. 33, Issue 20
Synthesis and Reactivity of Trivalent Tp*U(CH 2 Ph) 2 (THF): Insertion vs Oxidation at Low-Valent Uranium–Carbon Bonds
journal, January 2013
- Matson, Ellen M.; Forrest, William P.; Fanwick, Phillip E.
- Organometallics, Vol. 32, Issue 5
Uranium-mediated reductive conversion of CO2 to CO and carbonate in a single-vessel, closed synthetic cycle
journal, January 2012
- Schmidt, Anna-Corina; Nizovtsev, Alexey V.; Scheurer, Andreas
- Chemical Communications, Vol. 48, Issue 69
The Effect of Ligand Design on Metal Ion Spin State—Lessons from Spin Crossover Complexes
journal, May 2016
- Halcrow, Malcolm
- Crystals, Vol. 6, Issue 5
Uranium-mediated activation of small molecules
journal, January 2011
- Arnold, Polly L.
- Chemical Communications, Vol. 47, Issue 32
Single-ion 4f element magnetism: an ab-initio look at Ln(COT) 2 −
journal, January 2015
- Gendron, Frédéric; Pritchard, Benjamin; Bolvin, Hélène
- Dalton Transactions, Vol. 44, Issue 46
NBO 6.0 : Natural bond orbital analysis program
journal, March 2013
- Glendening, Eric D.; Landis, Clark R.; Weinhold, Frank
- Journal of Computational Chemistry, Vol. 34, Issue 16
Homoleptic Aryl Complexes of Uranium (IV)
journal, July 2019
- Wolford, Nikki J.; Sergentu, Dumitru‐Claudiu; Brennessel, William W.
- Angewandte Chemie International Edition, Vol. 58, Issue 30
Structural, Electrochemical, and Magnetic Studies of Bulky Uranium(III) and Uranium(IV) Metallocenes
journal, November 2019
- Boreen, Michael A.; Lussier, Daniel J.; Skeel, Brighton A.
- Inorganic Chemistry, Vol. 58, Issue 24
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
Synthesis and reactions of U(III) complexes with tripodal nitrogen and oxygen donor ligands
journal, October 1994
- McDonald, Robert; Sun, YiMin; Takats, Josef
- Journal of Alloys and Compounds, Vol. 213-214
Orbitals for Analyzing Bonding and Magnetism of Heavy-Metal Complexes
journal, September 2015
- Autschbach, Jochen
- Comments on Inorganic Chemistry, Vol. 36, Issue 4
Synthesis and Characterization of a Uranium(III) Complex Containing a Redox-Active 2,2′-Bipyridine Ligand
journal, February 2010
- Kraft, Steven J.; Fanwick, Phillip E.; Bart, Suzanne C.
- Inorganic Chemistry, Vol. 49, Issue 3
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
Generation of Tp*2U(N3) from a family of new uranium(III) alkyl complexes
journal, February 2018
- Tatebe, Caleb J.; Johnson, Sara A.; Zeller, Matthias
- Journal of Organometallic Chemistry, Vol. 857
Uranium(III) Complexes with Bulky Aryloxide Ligands Featuring Metal–Arene Interactions and Their Reactivity Toward Nitrous Oxide
journal, August 2013
- Franke, Sebastian M.; Tran, Ba L.; Heinemann, Frank W.
- Inorganic Chemistry, Vol. 52, Issue 18
Comparative EXAFS Investigation of Uranium(VI) and -(IV) Aquo Chloro Complexes in Solution Using a Newly Developed Spectroelectrochemical Cell
journal, September 2005
- Hennig, C.; Tutschku, J.; Rossberg, A.
- Inorganic Chemistry, Vol. 44, Issue 19
Natural transition orbitals
journal, March 2003
- Martin, Richard L.
- The Journal of Chemical Physics, Vol. 118, Issue 11