Equatorial ligand substitution by hydroxide in uranyl Pacman complexes of a Schiff-base pyrrole macrocycle

Polly L. Arnold, Dipti Patel, Anne-Frederique Pecharman, Claire Wilson, Jason B. Love

Research output: Contribution to journalArticlepeer-review

Abstract / Description of output

The synthesis of the mono-uranyl complex [UO2(THF)(H2LMe)] of a ditopic Schiff-base pyrrole macrocycle is described and is shown to adopt a Pacman wedge-shaped structure in which the uranyl dication is desymmetrised and sits solely in one N4-donor compartment to leave the other vacant. While investigating the mechanism of the previously reported, base-initiated, reductive silylation chemistry of [UO2(THF)(H2LMe)], we found that uranyl hydroxide complexes could be isolated. As such, the reaction between [UO2(THF)(H2LMe)] and KH in THF generated the dimeric cation-cation hydroxide [{UO2(OH)K(C6H6)(H2LMe)}2] when crystallised from C6H6, or alternatively, when crystallised from THF, the monomeric THF-adducted cation-cation complex [UO2(OH)K(THF)2(H2LMe)] was isolated. These compounds result formally from the substitution of the equatorial THF molecule by hydroxide, and it was also shown that the reaction between dry KOH and [UO2(THF)(H2LMe)] generated [{UO2(OH)K(C6H6)(H2LMe)}2].

Original languageEnglish
Pages (from-to)3501-3508
Number of pages8
JournalDalton Transactions
Volume39
Issue number14
Early online date2 Mar 2010
DOIs
Publication statusPublished - 14 Apr 2010

Keywords / Materials (for Non-textual outputs)

  • STEREOGNOSTIC COORDINATION CHEMISTRY
  • PENTAVALENT URANYL
  • ACTINYL IONS
  • URANIUM
  • DESIGN
  • GEOMETRIES
  • PROPERTY
  • NP(V)
  • ACID
  • OXO

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