An investigation of the electronic structure of some tris(η5-cyclopentadienyl)thorium(IV) and -uranium(IV) complexes by relativistic effective core potential ab initio calculations and gas-phase UV photoelectron spectroscopy

Santo Di Bella, Antonino Gulino, Giuseppe Lanza, Ignazio L. Fragalà, Tobin J Marks

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Abstract

Comparative relativistic effective core potential ab initio calculations for both Th(IV) and U(IV) Cp3AnL (Cp = η5-C5H5; L = CH3, BH4) complexes are reported. The Cp-An bonding appears to be dominated by metal 6d orbitals interacting with ligand π2 orbitals. Metal 5f orbitals provide a smaller contribution but are crucial for stabilization of the Cp3An cluster. The stability of the An-CH3 bonding depends upon interactions involving metal 6dz2-based orbitals directed along the An-CH3 vector. The L = BH4 ligand interactions are mediated by dxz and dyz atomic orbitals, which are even better suited for favorable overlap and, hence, for greater metal-ligand π covalency. Ground 3A2 states have been found to be the most stable for the U(IV) complexes. The experimental He I/He II photoelectron data are consistent with the quantum chemical calculations and indicate a close similarity between ground-state properties of the present Th(IV) and U(IV) complexes.

Original languageEnglish
Pages (from-to)11673-11676
Number of pages4
JournalJournal of Physical Chemistry
Volume97
Issue number45
Publication statusPublished - 1993

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Thorium
Uranium
thorium
Photoelectron spectroscopy
Ultraviolet spectroscopy
uranium
Electronic structure
Gases
Metals
photoelectron spectroscopy
vapor phases
electronic structure
orbitals
Ligands
Ground state
metals
ligands
Photoelectrons
ground state
Stabilization

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "An investigation of the electronic structure of some tris(η5-cyclopentadienyl)thorium(IV) and -uranium(IV) complexes by relativistic effective core potential ab initio calculations and gas-phase UV photoelectron spectroscopy",
abstract = "Comparative relativistic effective core potential ab initio calculations for both Th(IV) and U(IV) Cp3AnL (Cp = η5-C5H5; L = CH3, BH4) complexes are reported. The Cp-An bonding appears to be dominated by metal 6d orbitals interacting with ligand π2 orbitals. Metal 5f orbitals provide a smaller contribution but are crucial for stabilization of the Cp3An cluster. The stability of the An-CH3 bonding depends upon interactions involving metal 6dz2-based orbitals directed along the An-CH3 vector. The L = BH4 ligand interactions are mediated by dxz and dyz atomic orbitals, which are even better suited for favorable overlap and, hence, for greater metal-ligand π covalency. Ground 3A2 states have been found to be the most stable for the U(IV) complexes. The experimental He I/He II photoelectron data are consistent with the quantum chemical calculations and indicate a close similarity between ground-state properties of the present Th(IV) and U(IV) complexes.",
author = "{Di Bella}, Santo and Antonino Gulino and Giuseppe Lanza and Fragal{\`a}, {Ignazio L.} and Marks, {Tobin J}",
year = "1993",
language = "English",
volume = "97",
pages = "11673--11676",
journal = "Journal of Physical Chemistry",
issn = "0022-3654",
publisher = "American Chemical Society",
number = "45",

}

TY - JOUR

T1 - An investigation of the electronic structure of some tris(η5-cyclopentadienyl)thorium(IV) and -uranium(IV) complexes by relativistic effective core potential ab initio calculations and gas-phase UV photoelectron spectroscopy

AU - Di Bella, Santo

AU - Gulino, Antonino

AU - Lanza, Giuseppe

AU - Fragalà, Ignazio L.

AU - Marks, Tobin J

PY - 1993

Y1 - 1993

N2 - Comparative relativistic effective core potential ab initio calculations for both Th(IV) and U(IV) Cp3AnL (Cp = η5-C5H5; L = CH3, BH4) complexes are reported. The Cp-An bonding appears to be dominated by metal 6d orbitals interacting with ligand π2 orbitals. Metal 5f orbitals provide a smaller contribution but are crucial for stabilization of the Cp3An cluster. The stability of the An-CH3 bonding depends upon interactions involving metal 6dz2-based orbitals directed along the An-CH3 vector. The L = BH4 ligand interactions are mediated by dxz and dyz atomic orbitals, which are even better suited for favorable overlap and, hence, for greater metal-ligand π covalency. Ground 3A2 states have been found to be the most stable for the U(IV) complexes. The experimental He I/He II photoelectron data are consistent with the quantum chemical calculations and indicate a close similarity between ground-state properties of the present Th(IV) and U(IV) complexes.

AB - Comparative relativistic effective core potential ab initio calculations for both Th(IV) and U(IV) Cp3AnL (Cp = η5-C5H5; L = CH3, BH4) complexes are reported. The Cp-An bonding appears to be dominated by metal 6d orbitals interacting with ligand π2 orbitals. Metal 5f orbitals provide a smaller contribution but are crucial for stabilization of the Cp3An cluster. The stability of the An-CH3 bonding depends upon interactions involving metal 6dz2-based orbitals directed along the An-CH3 vector. The L = BH4 ligand interactions are mediated by dxz and dyz atomic orbitals, which are even better suited for favorable overlap and, hence, for greater metal-ligand π covalency. Ground 3A2 states have been found to be the most stable for the U(IV) complexes. The experimental He I/He II photoelectron data are consistent with the quantum chemical calculations and indicate a close similarity between ground-state properties of the present Th(IV) and U(IV) complexes.

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VL - 97

SP - 11673

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JF - Journal of Physical Chemistry

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