Oxo-Group-14-Element Bond Formation in Binuclear Uranium(V) Pacman Complexes

Guy M. Jones, Polly L. Arnold*, Jason B. Love

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

Simple and versatile routes to the functionalization of uranyl-derived U-V-oxo groups are presented. The oxo-lithiated, binuclear uranium(V)-oxo complexes [{(py)(3)LiOUO}(2)(L)] and [{(py)(3)LiOUO}(OUOSiMe3)(L)] were prepared by the direct combination of the uranyl(VI) silylamide ate complex [Li(py)(2)][(OUO)(N)(3)] (N=N(SiMe3)(2)) with the polypyrrolic macrocycle H4L or the mononuclear uranyl (VI) Pacman complex [UO2(py)(H2L)], respectively. These oxo-metalated complexes display distinct UO single and multiple bonding patterns and an axial/equatorial arrangement of oxo ligands. Their ready availability allows the direct functionalization of the uranyl oxo group leading to the binuclear uranium(V) oxo-stannylated complexes [{(R3Sn)OUO}(2)(L)] (R=nBu, Ph), which represent rare examples of mixed uranium/tin complexes. Also, uranium-oxo-group exchange occurred in reactions with [TiCl(OiPr)(3)] to form U-OC bonds [{(py)(3)LiOUO}(OUOiPr)(L)] and [(iPrOUO)(2)(L)]. Overall, these represent the first family of uranium(V) complexes that are oxo-functionalised by Group 14 elements.

Original languageEnglish
Pages (from-to)10287-10294
Number of pages8
JournalChemistry - A European Journal
Volume19
Issue number31
Early online date21 Jun 2013
DOIs
Publication statusPublished - 29 Jul 2013

Keywords

  • macrocyclic ligands
  • metalation
  • structure elucidation
  • synthesis design
  • uranium
  • VALENT ORGANOURANIUM COMPLEXES
  • PENTAVALENT URANYL COMPLEXES
  • CATION-CATION INTERACTIONS
  • OXO-FUNCTIONALIZATION
  • COORDINATION POLYMER
  • ELECTRONIC-STRUCTURE
  • CRYSTAL-STRUCTURE
  • ACTINYL IONS
  • SCHIFF-BASE
  • SILYLATION

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