Quantifying Actinide-Carbon Bond Covalency in a Uranyl-Aryl Complex Utilizing Solution 13C NMR Spectroscopy

Osvaldo Ordoñez; Xiaojuan Yu; Guang Wu; Jochen Autschbach; Trevor W. Hayton

doi:10.1021/acs.inorgchem.3c02440

Quantifying Actinide-Carbon Bond Covalency in a Uranyl-Aryl Complex Utilizing Solution ¹³C NMR Spectroscopy

Osvaldo Ordoñez
, Xiaojuan Yu
, Guang Wu
, Jochen Autschbach
, Trevor W. Hayton

Chemistry

University of California at Santa Barbara
SUNY Buffalo

Research output: Contribution to journal › Article › peer-review

12 Scopus citations

Abstract

Reaction of [UO₂Cl₂(THF)₂]₂ with in situ generated LiFmes (FmesH = 1,3,5-(CF₃)₃C₆H₃) in Et₂O resulted in the formation of the uranyl aryl complexes [Li(THF)₃][UO₂(Fmes)₃] ([Li(THF)₃][1]) and [Li(Et₂O)₃(THF)][UO₂(Fmes)₃] ([Li(Et₂O)₃(THF)][1]) in good to moderate yields after crystallization from hexanes and Et₂O, respectively. Both complexes were characterized by X-ray crystallography and NMR spectroscopy. DFT calculations reveal that the C_ispo resonance in [1]⁻ exhibits a deshielding of 51 ppm from spin-orbit coupling effects originating at uranium, which indicates an appreciable covalency in the U-C bonding interaction.

Original language	English
Pages (from-to)	9427-9433
Number of pages	7
Journal	Inorganic Chemistry
Volume	63
Issue number	21
DOIs	https://doi.org/10.1021/acs.inorgchem.3c02440
State	Published - May 27 2024

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title = "Quantifying Actinide-Carbon Bond Covalency in a Uranyl-Aryl Complex Utilizing Solution 13C NMR Spectroscopy",

abstract = "Reaction of [UO2Cl2(THF)2]2 with in situ generated LiFmes (FmesH = 1,3,5-(CF3)3C6H3) in Et2O resulted in the formation of the uranyl aryl complexes [Li(THF)3][UO2(Fmes)3] ([Li(THF)3][1]) and [Li(Et2O)3(THF)][UO2(Fmes)3] ([Li(Et2O)3(THF)][1]) in good to moderate yields after crystallization from hexanes and Et2O, respectively. Both complexes were characterized by X-ray crystallography and NMR spectroscopy. DFT calculations reveal that the Cispo resonance in [1]− exhibits a deshielding of 51 ppm from spin-orbit coupling effects originating at uranium, which indicates an appreciable covalency in the U-C bonding interaction.",

author = "Osvaldo Ordo{\~n}ez and Xiaojuan Yu and Guang Wu and Jochen Autschbach and Hayton, \{Trevor W.\}",

note = "Publisher Copyright: {\textcopyright} 2023 American Chemical Society.",

year = "2024",

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doi = "10.1021/acs.inorgchem.3c02440",

language = "English",

volume = "63",

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T1 - Quantifying Actinide-Carbon Bond Covalency in a Uranyl-Aryl Complex Utilizing Solution 13C NMR Spectroscopy

AU - Ordoñez, Osvaldo

AU - Yu, Xiaojuan

AU - Wu, Guang

AU - Autschbach, Jochen

AU - Hayton, Trevor W.

PY - 2024/5/27

Y1 - 2024/5/27

N2 - Reaction of [UO2Cl2(THF)2]2 with in situ generated LiFmes (FmesH = 1,3,5-(CF3)3C6H3) in Et2O resulted in the formation of the uranyl aryl complexes [Li(THF)3][UO2(Fmes)3] ([Li(THF)3][1]) and [Li(Et2O)3(THF)][UO2(Fmes)3] ([Li(Et2O)3(THF)][1]) in good to moderate yields after crystallization from hexanes and Et2O, respectively. Both complexes were characterized by X-ray crystallography and NMR spectroscopy. DFT calculations reveal that the Cispo resonance in [1]− exhibits a deshielding of 51 ppm from spin-orbit coupling effects originating at uranium, which indicates an appreciable covalency in the U-C bonding interaction.

AB - Reaction of [UO2Cl2(THF)2]2 with in situ generated LiFmes (FmesH = 1,3,5-(CF3)3C6H3) in Et2O resulted in the formation of the uranyl aryl complexes [Li(THF)3][UO2(Fmes)3] ([Li(THF)3][1]) and [Li(Et2O)3(THF)][UO2(Fmes)3] ([Li(Et2O)3(THF)][1]) in good to moderate yields after crystallization from hexanes and Et2O, respectively. Both complexes were characterized by X-ray crystallography and NMR spectroscopy. DFT calculations reveal that the Cispo resonance in [1]− exhibits a deshielding of 51 ppm from spin-orbit coupling effects originating at uranium, which indicates an appreciable covalency in the U-C bonding interaction.

UR - https://www.scopus.com/pages/publications/85175958620

U2 - 10.1021/acs.inorgchem.3c02440

DO - 10.1021/acs.inorgchem.3c02440

M3 - Article

C2 - 37788299

AN - SCOPUS:85175958620

SN - 0020-1669

VL - 63

SP - 9427

EP - 9433

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 21

ER -

Quantifying Actinide-Carbon Bond Covalency in a Uranyl-Aryl Complex Utilizing Solution ¹³C NMR Spectroscopy

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