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

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

14 Scopus citations

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 (US)
Pages (from-to)11673-11676
Number of pages4
JournalJournal of physical chemistry
Volume97
Issue number45
DOIs
StatePublished - Jan 1 1993

ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

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