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Theoretical Design of cis ‐Bis(imido)uranium Iodides – Electronic Structures and Spectroscopic Properties

To understand the structural and electronic properties of uranium complexes, the ‐bis(imido)uranium iodides ‐[U(NPh)(THF)I] (Ph) and ‐[U(NPh)(THF)I] (Ph) have been designed, and their structures and properties have been calculated by density functional theory (DFT) and time‐dependent DFT. Four isome... Full description

Journal Title: European Journal of Inorganic Chemistry October 2014, Vol.2014(30), pp.5168-5176
Main Author: Lv, Chun‐Mei
Other Authors: Pan, Ling‐Chao , Pan, Qing‐Jiang , Guo, Yuan‐Ru , Zhang, Hong‐Xing
Format: Electronic Article Electronic Article
Language: English
Subjects:
ID: ISSN: 1434-1948 ; E-ISSN: 1099-0682 ; DOI: 10.1002/ejic.201402505
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recordid: wj10.1002/ejic.201402505
title: Theoretical Design of cis ‐Bis(imido)uranium Iodides – Electronic Structures and Spectroscopic Properties
format: Article
creator:
  • Lv, Chun‐Mei
  • Pan, Ling‐Chao
  • Pan, Qing‐Jiang
  • Guo, Yuan‐Ru
  • Zhang, Hong‐Xing
subjects:
  • Uranium
  • N Ligands
  • Electronic Structure
  • Absorption Spectroscopy
  • Density Functional Calculations
ispartof: European Journal of Inorganic Chemistry, October 2014, Vol.2014(30), pp.5168-5176
description: To understand the structural and electronic properties of uranium complexes, the ‐bis(imido)uranium iodides ‐[U(NPh)(THF)I] (Ph) and ‐[U(NPh)(THF)I] (Ph) have been designed, and their structures and properties have been calculated by density functional theory (DFT) and time‐dependent DFT. Four isomers (Ph1, Ph2, Ph1, Ph2) were addressed in the study; these isomers have the structural feature that one iodide atom is to one imido group in the axial direction, and the other iodine atom is to the other imido group in the equatorial plane. The total system energies, geometry parameters, and vibrational spectra were similar among the respective isomers. Analyses of the electronic structures in tetrahydrofuran solution revealed that these isomeric complexes show mixed π(U=N) and π(Ph) character for the highest occupied molecular orbital (HOMO) and HOMO–1; the lone pairs of electrons of the iodine atom are dominant in the energetically lower occupied orbitals. U(f)‐type orbitals contribute to the low‐lying unoccupied orbitals, as has been generally accepted for analogous hexavalent ‐dioxouranium complexes. Three main absorption peaks were observed for Ph1/Ph2 and Ph1/Ph2 from time‐dependent long‐range‐corrected functional calculations. The first one originates from the π(U=N) bonds and the phenyl groups, and the third is related to character of the iodine atoms [σ(U–I) and π(I)]; combined π(I) and π(U=N) character is attributed to the middle peak. We also calculated the experimentally known ‐U(NPh)(THF)I (‐Ph). The comparison of ‐Ph, Ph1, and Ph2 indicates that the / isomerism has a relatively large effect on their structural and electronic properties. The electronic and spectroscopic properties of ‐bis(imido)uranium iodides have been explored by DFT. A mixed π(U=N) and π(Ph) character was calculated for their highest occupied molecular orbitals. Each U=N bond forms one orbital, which contributes to the bent N=U=N molecular skeleton. The delocalized character of the N=U=N unit in the corresponding isomer allows its linear structure.
language: eng
source:
identifier: ISSN: 1434-1948 ; E-ISSN: 1099-0682 ; DOI: 10.1002/ejic.201402505
fulltext: fulltext
issn:
  • 1434-1948
  • 14341948
  • 1099-0682
  • 10990682
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titleTheoretical Design of cis ‐Bis(imido)uranium Iodides – Electronic Structures and Spectroscopic Properties
creatorLv, Chun‐Mei ; Pan, Ling‐Chao ; Pan, Qing‐Jiang ; Guo, Yuan‐Ru ; Zhang, Hong‐Xing
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subjectUranium ; N Ligands ; Electronic Structure ; Absorption Spectroscopy ; Density Functional Calculations
descriptionTo understand the structural and electronic properties of uranium complexes, the ‐bis(imido)uranium iodides ‐[U(NPh)(THF)I] (Ph) and ‐[U(NPh)(THF)I] (Ph) have been designed, and their structures and properties have been calculated by density functional theory (DFT) and time‐dependent DFT. Four isomers (Ph1, Ph2, Ph1, Ph2) were addressed in the study; these isomers have the structural feature that one iodide atom is to one imido group in the axial direction, and the other iodine atom is to the other imido group in the equatorial plane. The total system energies, geometry parameters, and vibrational spectra were similar among the respective isomers. Analyses of the electronic structures in tetrahydrofuran solution revealed that these isomeric complexes show mixed π(U=N) and π(Ph) character for the highest occupied molecular orbital (HOMO) and HOMO–1; the lone pairs of electrons of the iodine atom are dominant in the energetically lower occupied orbitals. U(f)‐type orbitals contribute to the low‐lying unoccupied orbitals, as has been generally accepted for analogous hexavalent ‐dioxouranium complexes. Three main absorption peaks were observed for Ph1/Ph2 and Ph1/Ph2 from time‐dependent long‐range‐corrected functional calculations. The first one originates from the π(U=N) bonds and the phenyl groups, and the third is related to character of the iodine atoms [σ(U–I) and π(I)]; combined π(I) and π(U=N) character is attributed to the middle peak. We also calculated the experimentally known ‐U(NPh)(THF)I (‐Ph). The comparison of ‐Ph, Ph1, and Ph2 indicates that the / isomerism has a relatively large effect on their structural and electronic properties. The electronic and spectroscopic properties of ‐bis(imido)uranium iodides have been explored by DFT. A mixed π(U=N) and π(Ph) character was calculated for their highest occupied molecular orbitals. Each U=N bond forms one orbital, which contributes to the bent N=U=N molecular skeleton. The delocalized character of the N=U=N unit in the corresponding isomer allows its linear structure.
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titleTheoretical Design of cis ‐Bis(imido)uranium Iodides – Electronic Structures and Spectroscopic Properties
descriptionTo understand the structural and electronic properties of uranium complexes, the ‐bis(imido)uranium iodides ‐[U(NPh)(THF)I] (Ph) and ‐[U(NPh)(THF)I] (Ph) have been designed, and their structures and properties have been calculated by density functional theory (DFT) and time‐dependent DFT. Four isomers (Ph1, Ph2, Ph1, Ph2) were addressed in the study; these isomers have the structural feature that one iodide atom is to one imido group in the axial direction, and the other iodine atom is to the other imido group in the equatorial plane. The total system energies, geometry parameters, and vibrational spectra were similar among the respective isomers. Analyses of the electronic structures in tetrahydrofuran solution revealed that these isomeric complexes show mixed π(U=N) and π(Ph) character for the highest occupied molecular orbital (HOMO) and HOMO–1; the lone pairs of electrons of the iodine atom are dominant in the energetically lower occupied orbitals. U(f)‐type orbitals contribute to the low‐lying unoccupied orbitals, as has been generally accepted for analogous hexavalent ‐dioxouranium complexes. Three main absorption peaks were observed for Ph1/Ph2 and Ph1/Ph2 from time‐dependent long‐range‐corrected functional calculations. The first one originates from the π(U=N) bonds and the phenyl groups, and the third is related to character of the iodine atoms [σ(U–I) and π(I)]; combined π(I) and π(U=N) character is attributed to the middle peak. We also calculated the experimentally known ‐U(NPh)(THF)I (‐Ph). The comparison of ‐Ph, Ph1, and Ph2 indicates that the / isomerism has a relatively large effect on their structural and electronic properties. The electronic and spectroscopic properties of ‐bis(imido)uranium iodides have been explored by DFT. A mixed π(U=N) and π(Ph) character was calculated for their highest occupied molecular orbitals. Each U=N bond forms one orbital, which contributes to the bent N=U=N molecular skeleton. The delocalized character of the N=U=N unit in the corresponding isomer allows its linear structure.
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abstractTo understand the structural and electronic properties of uranium complexes, the ‐bis(imido)uranium iodides ‐[U(NPh)(THF)I] (Ph) and ‐[U(NPh)(THF)I] (Ph) have been designed, and their structures and properties have been calculated by density functional theory (DFT) and time‐dependent DFT. Four isomers (Ph1, Ph2, Ph1, Ph2) were addressed in the study; these isomers have the structural feature that one iodide atom is to one imido group in the axial direction, and the other iodine atom is to the other imido group in the equatorial plane. The total system energies, geometry parameters, and vibrational spectra were similar among the respective isomers. Analyses of the electronic structures in tetrahydrofuran solution revealed that these isomeric complexes show mixed π(U=N) and π(Ph) character for the highest occupied molecular orbital (HOMO) and HOMO–1; the lone pairs of electrons of the iodine atom are dominant in the energetically lower occupied orbitals. U(f)‐type orbitals contribute to the low‐lying unoccupied orbitals, as has been generally accepted for analogous hexavalent ‐dioxouranium complexes. Three main absorption peaks were observed for Ph1/Ph2 and Ph1/Ph2 from time‐dependent long‐range‐corrected functional calculations. The first one originates from the π(U=N) bonds and the phenyl groups, and the third is related to character of the iodine atoms [σ(U–I) and π(I)]; combined π(I) and π(U=N) character is attributed to the middle peak. We also calculated the experimentally known ‐U(NPh)(THF)I (‐Ph). The comparison of ‐Ph, Ph1, and Ph2 indicates that the / isomerism has a relatively large effect on their structural and electronic properties. The electronic and spectroscopic properties of ‐bis(imido)uranium iodides have been explored by DFT. A mixed π(U=N) and π(Ph) character was calculated for their highest occupied molecular orbitals. Each U=N bond forms one orbital, which contributes to the bent N=U=N molecular skeleton. The delocalized character of the N=U=N unit in the corresponding isomer allows its linear structure.
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doi10.1002/ejic.201402505
pages5168-5176
date2014-10