Organo-f-element thermochemistry.  Thorium vs. uranium and ancillary ligand effects on metal-ligand bond disruption enthalpies in bis(pentamethylcyclopentadienyl)actinide bis(hydrocarbyls) and bis(pentamethylcyclopentadienyl) alkoxy actinide hydrides and hydrocarbyls

Bruno, Joseph W.; Stecher, Hilmar A.; Morss, Lester R.; Sonnenberger, David C.; Marks, Tobin J.

doi:10.1021/ja00283a023

Cited by 79 publications

(46 citation statements)

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“…The decreasing UX bond strengths for heavier halogen ligands is due to the decreased steric interaction between U and X, as a result of the elongated UX bonds. The decreased N–M(2) bond order and bond energies are consistent with the general trend of the bond dissociation energies from UX 41. The trend of the UX bond strength in UX 5 − also follows the typical Badger‐rule behavior,42 that is, a longer bond results in a weaker bond energy.…”

Section: Resultssupporting

confidence: 80%

“…The decreased N-M(2) bond order and bond energies are consistent with the general trend of the bond dissociation energies from U À X. [41] The trend of the UÀX bond strength in UX 5 À also follows the typical Badger-rule behavior, [42] that is, a longer bond results in a weaker bond energy. Therefore, the increasing UÀX covalency from X = F to I does not guarantee a stronger bond because both ionic and covalent interactions are important.…”

Section: Ionic Vs Covalent Bondingsupporting

confidence: 72%

“…The covalent interaction almost doubles from UÀ F (13.8 %) to UÀCl (25.6 %) and increases to 30.6 % for UÀ I. [41] The trend of the UÀX bond strength in UX 5 À also follows the typical Badger-rule behavior, [42] that is, a longer bond results in a weaker bond energy. The covalency of the actinide-chlorine bonding has been previously discussed based on chlorine K-edge X-ray absorption spectroscopy (XAS) and groundstate and time-dependent hybrid density functional theory.…”

Section: Ionic Vs Covalent Bondingmentioning

confidence: 80%

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A Joint Photoelectron Spectroscopy and Theoretical Study on the Electronic Structure of UCl₅⁻ and UCl₅

Dau

et al. 2013

Chemistry An Asian Journal

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We report a combined photoelectron spectroscopic and relativistic quantum chemistry study on gaseous UCl5(-) and UCl5. The UCl5(-) anion is produced using electrospray ionization and found to be highly electronically stable with an adiabatic electron binding energy of 4.76±0.03 eV, which also represents the electron affinity of the neutral UCl5 molecule. Theoretical investigations reveal that the ground state of UCl5(-) has an open shell with two unpaired electrons occupying two primarily U 5f(z³) and 5f(xyz) based molecular orbitals. The structures of both UCl5(-) and UCl5 are theoretically optimized and confirmed to have C(4v) symmetry. The computational results are in good agreement with the photoelectron spectra, providing insights into the electronic structures and valence molecular orbitals of UCl5(-) and UCl5. We also performed systematic theoretical studies on all the uranium pentahalide complexes UX5(-) (X=F, Cl, Br, I). Chemical bonding analyses indicate that the U-X interactions in UX5(-) are dominated by ionic bonding, with increasing covalent contributions for the heavier halogen complexes.

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Section: Resultssupporting

confidence: 80%

Section: Ionic Vs Covalent Bondingsupporting

confidence: 72%

Section: Ionic Vs Covalent Bondingmentioning

confidence: 80%

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A Joint Photoelectron Spectroscopy and Theoretical Study on the Electronic Structure of UCl₅⁻ and UCl₅

Dau

et al. 2013

Chemistry An Asian Journal

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“…Thermochemische Untersuchungen haben gezeigt, dass die Spaltungsenthalpien für Uran‐Kohlenstoff‐Bindungen 70–90 kcal mol −1 betragen 46. Daraus kann gefolgert werden, dass Uran‐Ligand‐Verknüpfungen thermodynamisch nicht instabil sind.…”

Section: Periodizität Und Physikochemische Eigenschaftenunclassified

Die Renaissance der nichtwässrigen Uranchemie

Liddle

2015

Angewandte Chemie

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Bis zum Jahr 2000 umfasste die nichtwässrige Uranchemie hauptsächlich Metallocen‐ und klassische Alkyl‐, Amid‐ oder Alkoxidverbindungen sowie bekannte Carben‐, Imido‐ und Oxoderivate. Seither hat das Gebiet einen starken Aufschwung erfahren, einhergehend mit der Entwicklung von Hilfsliganden, mehrfach bindenden Ligandenarten, der Aktivierung niedermolekularer Verbindungen und der Untersuchung magnetischer Eigenschaften. Dieser Aufsatz führt in die theoretischen Grundlagen des Gebiets ein, behandelt wichtige Ausgangsstoffe und untersucht neuere Ligandenklassen für Uran, einschließlich Alkyle, Aryle, Arene, Carbene, Amide, Imide, Nitride, Alkoxide, Aryloxide und Oxoeinheiten. Des Weiteren werden die Fortschritte auf dem Gebiet des Einzelmolekülmagnetismus beschrieben, bevor eine Zusammenfassung der Koordination und Aktivierung niedermolekularer Verbindungen, einschließlich Kohlenmonoxid, Kohlendioxid, Stickstoffmonoxid, Distickstoff, weißem Phosphor und Alkanen, gegeben wird.

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“…Thermochemical studies have shown the uranium–carbon bond disruption enthalpies to be approximately 70–90 kcal mol −1 46. Therefore, it can be concluded that there is nothing thermodynamically unstable about uranium–ligand linkages.…”

Section: Periodicity and Physicochemical Propertiesmentioning

confidence: 99%

Water‐Soluble Luminescent Cyclometalated Gold(III) Complexes with cis‐Chelating Bis(N‐Heterocyclic Carbene) Ligands: Synthesis and Photophysical Properties

Hung

Zhang

et al. 2014

Chemistry A European J

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A new class of cyclometalated Au(III) complexes containing various bidentate C-deprotonated C^N and cis-chelating bis(N-heterocyclic carbene) (bis-NHC) ligands has been synthesized and characterized. These are the first examples of Au(III) complexes supported by cis-chelating bis-NHC ligands. [Au(C^N)(bis-NHC)] complexes display emission in solutions under degassed condition at room temperature with emission maxima (λmax ) at 498-633 nm and emission quantum yields of up to 10.1 %. The emissions are assigned to triplet intraligand (IL) π→π* transitions of C^N ligands. The Au(III) complex containing a C^N (C-deprotonated naphthalene-substituted quinoline) ligand with extended π-conjugation exhibits prompt fluorescence and phosphorescence of comparable intensity with λmax at 454 and 611 nm respectively. With sulfonate-functionalized bis-NHC ligand, four water-soluble luminescent Au(III) complexes, including those displaying both fluorescence and phosphorescence, were prepared. They show similar photophysical properties in water when compared with their counterparts in acetonitrile. The long phosphorescence lifetime of the water-soluble AuIII complex with C-deprotonated naphthalene-substituted quinoline ligand renders it to function as ratiometric sensor for oxygen. Inhibitory activity of one of these water-soluble Au(III) complexes towards deubiquitinase (DUB) UCHL3 has been investigated; this complex also displayed a significant inhibitory activity with IC50 value of 0.15 μM.

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Organo-f-element thermochemistry. Thorium vs. uranium and ancillary ligand effects on metal-ligand bond disruption enthalpies in bis(pentamethylcyclopentadienyl)actinide bis(hydrocarbyls) and bis(pentamethylcyclopentadienyl) alkoxy actinide hydrides and hydrocarbyls

Cited by 79 publications

References 1 publication

A Joint Photoelectron Spectroscopy and Theoretical Study on the Electronic Structure of UCl₅⁻ and UCl₅

A Joint Photoelectron Spectroscopy and Theoretical Study on the Electronic Structure of UCl₅⁻ and UCl₅

Die Renaissance der nichtwässrigen Uranchemie

Water‐Soluble Luminescent Cyclometalated Gold(III) Complexes with cis‐Chelating Bis(N‐Heterocyclic Carbene) Ligands: Synthesis and Photophysical Properties

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Organo-f-element thermochemistry. Thorium vs. uranium and ancillary ligand effects on metal-ligand bond disruption enthalpies in bis(pentamethylcyclopentadienyl)actinide bis(hydrocarbyls) and bis(pentamethylcyclopentadienyl) alkoxy actinide hydrides and hydrocarbyls

Cited by 79 publications

References 1 publication

A Joint Photoelectron Spectroscopy and Theoretical Study on the Electronic Structure of UCl5− and UCl5

A Joint Photoelectron Spectroscopy and Theoretical Study on the Electronic Structure of UCl5− and UCl5

Die Renaissance der nichtwässrigen Uranchemie

Water‐Soluble Luminescent Cyclometalated Gold(III) Complexes with cis‐Chelating Bis(N‐Heterocyclic Carbene) Ligands: Synthesis and Photophysical Properties

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Product

Resources

About

A Joint Photoelectron Spectroscopy and Theoretical Study on the Electronic Structure of UCl₅⁻ and UCl₅

A Joint Photoelectron Spectroscopy and Theoretical Study on the Electronic Structure of UCl₅⁻ and UCl₅