Photoelectron spectroscopy of f-element organometallic complexes. 8. DV-Xα and gas-phase UV photoelectron spectroscopic investigation of the electronic structure of tris(η5-cyclopentadienyl)uranium(IV) complexes

Antonino Gulino, Enrico Ciliberto, Santo Di Bella, Ignazio Fragalà, Afif M. Seyam, Tobin J Marks

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

The electronic structures of a series of closely related U(η5-C5H5)3L (L = -CH3, -NH2, -BH4, -NCS) complexes has been studied using the SCF Hartree-Fock-Slater first-principles discrete variational Xα method in combination with He I and He II UV photoelectron spectroscopy. The theoretical results reproduce the experimental He I and He II photoelectron spectroscopic data, thus providing a reliable description of the metal-ligand bonding. Symmetry considerations render the 5f elements well-suited templates for coordination of the Cp3 ligand cluster. Interactions not restricted by symmetry appear partially or entirely modulated by the angular properties of π2-related MO's. Bonding interactions with ancillary L ligands involve either 5fz3 or 6dz2 metal orbitals, depending upon the energies of the unperturbed ligand orbital counterparts. Metal-ligand interactions cause the energies of 5f orbitals to split into a narrow manifold with a remarkable "ligand field" energy shift associated only with the 5fy(3x2-y2) orbital. The L→M charge donation results in an electronic configuration of the uranium atom which is almost constant throughout the U(C5H5)3L series and similar to that found in a fully relativistic SCF Dirac-Slater calculation on the simpler uranium atom. The stringent necessity of maintaining the uranium center in a particularly stable electronic configuration causes greater donation (hence larger covalency in the bonding) from ancillary L ligands to be compensated for by an increasing (L = -NH2 <-CH3 <-NCS <BH4-) ionic character of the U-Cp bonds. The present results show that nonrelativistic DV-Xα calculations, optimized for basis set and potential representation, reproduce experimental photoelectron spectroscopic data, including He I/He II relative intensity changes.

Original languageEnglish
Pages (from-to)3248-3257
Number of pages10
JournalOrganometallics
Volume11
Issue number10
Publication statusPublished - 1992

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Uranium
Organometallics
Photoelectron spectroscopy
Photoelectrons
uranium
Electronic structure
photoelectrons
Gases
photoelectron spectroscopy
vapor phases
electronic structure
Ligands
ligands
orbitals
Metals
self consistent fields
metals
Atoms
causes
interactions

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Photoelectron spectroscopy of f-element organometallic complexes. 8. DV-Xα and gas-phase UV photoelectron spectroscopic investigation of the electronic structure of tris(η5-cyclopentadienyl)uranium(IV) complexes. / Gulino, Antonino; Ciliberto, Enrico; Di Bella, Santo; Fragalà, Ignazio; Seyam, Afif M.; Marks, Tobin J.

In: Organometallics, Vol. 11, No. 10, 1992, p. 3248-3257.

Research output: Contribution to journalArticle

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abstract = "The electronic structures of a series of closely related U(η5-C5H5)3L (L = -CH3, -NH2, -BH4, -NCS) complexes has been studied using the SCF Hartree-Fock-Slater first-principles discrete variational Xα method in combination with He I and He II UV photoelectron spectroscopy. The theoretical results reproduce the experimental He I and He II photoelectron spectroscopic data, thus providing a reliable description of the metal-ligand bonding. Symmetry considerations render the 5f elements well-suited templates for coordination of the Cp3 ligand cluster. Interactions not restricted by symmetry appear partially or entirely modulated by the angular properties of π2-related MO's. Bonding interactions with ancillary L ligands involve either 5fz3 or 6dz2 metal orbitals, depending upon the energies of the unperturbed ligand orbital counterparts. Metal-ligand interactions cause the energies of 5f orbitals to split into a narrow manifold with a remarkable {"}ligand field{"} energy shift associated only with the 5fy(3x2-y2) orbital. The L→M charge donation results in an electronic configuration of the uranium atom which is almost constant throughout the U(C5H5)3L series and similar to that found in a fully relativistic SCF Dirac-Slater calculation on the simpler uranium atom. The stringent necessity of maintaining the uranium center in a particularly stable electronic configuration causes greater donation (hence larger covalency in the bonding) from ancillary L ligands to be compensated for by an increasing (L = -NH2 <-CH3 <-NCS <BH4-) ionic character of the U-Cp bonds. The present results show that nonrelativistic DV-Xα calculations, optimized for basis set and potential representation, reproduce experimental photoelectron spectroscopic data, including He I/He II relative intensity changes.",
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