Synthesis and Characterization of Two Uranyl-Aryl “Ate” Complexes

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

doi:10.1002/chem.202005078

Synthesis and Characterization of Two Uranyl-Aryl “Ate” Complexes

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

18 Scopus citations

Abstract

Reaction of [UO₂Cl₂(THF)₃] with 3 equivalents of LiC₆Cl₅ in Et₂O resulted in the formation of first uranyl aryl complex [Li(Et₂O)₂(THF)][UO₂(C₆Cl₅)₃] ([Li][1]) in good yields. Subsequent dissolution of [Li][1] in THF resulted in conversion into [Li(THF)₄][UO₂(C₆Cl₅)₃(THF)] ([Li][2]), also in good yields. DFT calculations reveal that the U−C bonds in [Li][1] and [Li][2] exhibit appreciable covalency. Additionally, the ¹³C NMR chemical shifts for their C_ipso environments are strongly affected by spin-orbit coupling—a consequence of 5f orbital participation in the U−C bonds.

Original language	English
Pages (from-to)	5885-5889
Number of pages	5
Journal	Chemistry - A European Journal
Volume	27
Issue number	19
DOIs	https://doi.org/10.1002/chem.202005078
State	Published - Apr 1 2021

Keywords

actinides
chemical shift
covalency
density functional calculations
uranyl organometallic

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10.1002/chem.202005078

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title = "Synthesis and Characterization of Two Uranyl-Aryl “Ate” Complexes",

abstract = "Reaction of [UO2Cl2(THF)3] with 3 equivalents of LiC6Cl5 in Et2O resulted in the formation of first uranyl aryl complex [Li(Et2O)2(THF)][UO2(C6Cl5)3] ([Li][1]) in good yields. Subsequent dissolution of [Li][1] in THF resulted in conversion into [Li(THF)4][UO2(C6Cl5)3(THF)] ([Li][2]), also in good yields. DFT calculations reveal that the U−C bonds in [Li][1] and [Li][2] exhibit appreciable covalency. Additionally, the 13C NMR chemical shifts for their Cipso environments are strongly affected by spin-orbit coupling—a consequence of 5f orbital participation in the U−C bonds.",

keywords = "actinides, chemical shift, covalency, density functional calculations, uranyl organometallic",

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

note = "Publisher Copyright: {\textcopyright} 2020 Wiley-VCH GmbH",

year = "2021",

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doi = "10.1002/chem.202005078",

language = "English",

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T1 - Synthesis and Characterization of Two Uranyl-Aryl “Ate” Complexes

AU - Ordoñez, Osvaldo

AU - Yu, Xiaojuan

AU - Wu, Guang

AU - Autschbach, Jochen

AU - Hayton, Trevor W.

PY - 2021/4/1

Y1 - 2021/4/1

N2 - Reaction of [UO2Cl2(THF)3] with 3 equivalents of LiC6Cl5 in Et2O resulted in the formation of first uranyl aryl complex [Li(Et2O)2(THF)][UO2(C6Cl5)3] ([Li][1]) in good yields. Subsequent dissolution of [Li][1] in THF resulted in conversion into [Li(THF)4][UO2(C6Cl5)3(THF)] ([Li][2]), also in good yields. DFT calculations reveal that the U−C bonds in [Li][1] and [Li][2] exhibit appreciable covalency. Additionally, the 13C NMR chemical shifts for their Cipso environments are strongly affected by spin-orbit coupling—a consequence of 5f orbital participation in the U−C bonds.

AB - Reaction of [UO2Cl2(THF)3] with 3 equivalents of LiC6Cl5 in Et2O resulted in the formation of first uranyl aryl complex [Li(Et2O)2(THF)][UO2(C6Cl5)3] ([Li][1]) in good yields. Subsequent dissolution of [Li][1] in THF resulted in conversion into [Li(THF)4][UO2(C6Cl5)3(THF)] ([Li][2]), also in good yields. DFT calculations reveal that the U−C bonds in [Li][1] and [Li][2] exhibit appreciable covalency. Additionally, the 13C NMR chemical shifts for their Cipso environments are strongly affected by spin-orbit coupling—a consequence of 5f orbital participation in the U−C bonds.

KW - actinides

KW - chemical shift

KW - covalency

KW - density functional calculations

KW - uranyl organometallic

UR - https://www.scopus.com/pages/publications/85099473019

U2 - 10.1002/chem.202005078

DO - 10.1002/chem.202005078

M3 - Article

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AN - SCOPUS:85099473019

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EP - 5889

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 19

ER -

Synthesis and Characterization of Two Uranyl-Aryl “Ate” Complexes

Abstract

Keywords

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