Thorium(IV) alkyl synthesis from a thorium(III) cyclopentadienyl complex and an Nheterocyclic olefin

Research output: Contribution to journalArticle

  • External authors:
  • Jingjing Liu
  • John Seed
  • Alasdair Formanuik
  • Fabrizio Ortu
  • Ashley Wooles

Abstract

Treatment of the tris(cyclopentadienyl) thorium(III) complex [Th(η5-Cp′′)3] [1, Cp′′ = C5H3-1,3- (SiMe3)2] with the N-heterocyclic olefin H2C=C(NMeCH)2 (2) reproducibly produces the thorium(IV)-methyl derivative [Th(η5-Cp′′)3(Me)] (3) along with MeImCH2CH2ImMe (Im = imidazole). The reaction mechanism, which is consistent with 1H NMR spectroscopic observations, is proposed to proceed via: (i) coordination of 2 to 1; (ii) one-electron transfer from thorium to 2; (iii) N-methyl cleavage and transfer to thorium to give 3; (iv) coupling of the resulting imidazolium radical by-product to give MeImCH2CH2ImMe. Complex 3 has been characterised by single crystal X-ray diffraction, multi-nuclear NMR and IR spectroscopies, and elemental analyses, and MeImCH2CH2ImMe by 1H NMR spectroscopy and mass spectrometry.

Bibliographical metadata

Original languageEnglish
JournalJournal of Organometallic Chemistry
Early online date26 Aug 2017
DOIs
Publication statusPublished - 2017

Related information