The Effect of the Equatorial Environment on Oxo-Group Silylation of the Uranyl Dication: A Computational Study

Ahmed Yahia, Polly L. Arnold, Jason B. Love, Laurent Maron

Research output: Contribution to journalArticlepeer-review

Abstract

A theoretical investigation of the reductive oxo-group silylation reaction of the uranyl dication held in a Pacman macrocylic environment has been carried out. The effect of the modeling of the Pacman ligand on the reaction profiles is found to be important, with the dipotassiation of a single oxo group identified as a key component in promoting the reaction between the Si X and uranium-oxo bonds. This reductive silylation reaction is also proposed to occur in an aqueous environment but was found not to operate on bare ions; in this latter case, substitution of a ligand in the equatorial plane was the most likely reaction. These results demonstrate the importance of the presence but not the identity of the equatorial ligands upon the silylation of the uranyl U-O bond.

Original languageEnglish
Pages (from-to)4881-4888
Number of pages8
JournalChemistry - A European Journal
Volume16
Issue number16
Early online date18 Mar 2010
DOIs
Publication statusPublished - 26 Apr 2010

Keywords

  • density functional calculations
  • equatorial ligands
  • macrocycles
  • silylation
  • uranium
  • HYDROXIDE COMPLEXES
  • ACTINIDE ELEMENTS
  • BASIS-SETS
  • REDUCTION
  • URANIUM
  • WATER
  • IONS
  • PSEUDOPOTENTIALS
  • COORDINATION
  • REACTIVITY

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