A Molecular Orbital Study of Bonding and Ionization Energies in Pentavalent Uranium Imide/Amide Complexes

G. A. Bowmaker, A. Gorling, O. Haberlen, N. Rösch*, G. L. Goodman, Donald E Ellis

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

7 Scopus citations

Abstract

Discrete variational local density functional (Xα) calculations on the model complexes [(RN)U(NR2)3] (R = H (1), SiH3(2)) have been performed in order to investigate the electronic structure of uranium amido/imido complexes. Special emphasis is placed on the energy ordering of the highest lying levels formed by U 5f orbitals and by out-of-plane N 2pπorbitals. Orbital relaxations are also estimated by studying the fragments NR and NR2with R = H and R = SiMe3in order to allow a comparison of the model compounds 1 and 2 with the measured photoelectron spectrum of the complex |(Me3SiN)U[N(SiMe3)2]3). The ionization energies corresponding to the N 2pπMOs are calculated in the order N 2pπ(amido) < N 2pπ(imido). The calculated level ordering is rationalized by comparing the order of the two types of U-N bonds and the charge distributions of the corresponding ligands. Taking the calculated ordering as well as the character of the molecular orbitals into account, a new assignment of the observed photoelectron spectra is given based on a comparison of He I and He II spectra.

Original languageEnglish (US)
Pages (from-to)577-581
Number of pages5
JournalInorganic Chemistry
Volume31
Issue number4
DOIs
StatePublished - Feb 1 1992

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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