Room-Temperature Synthesis of (LiMo3Se3)n and the Determination of the Relative Reduction Potential of tert-Butyllithium

Josh H. Golden*, Francis J. DiSalvo, Jean M.J. Fréchet

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

10 Scopus citations

Abstract

A room-temperature synthesis of the inorganic polymer (LiMo3Se3)n by reductive intercalation is described. Instead of the traditional preparation by ion exchange at approximately 460 °C, (LiMo3Se3)n was prepared by treating (InMo3Se3)n with a 10-fold excess of tert-butyllithium in pentane/toluene at 23 °C for 1 week. While there is some reductive attack of the (Mo3Se3-)n chain core, reductive intercalation of lithium competed successfully to form (LiMo3Se3)n, as confirmed by X-ray powder diffraction, TEM, SEM microprobe, and product solubility in polar solvents. Proton NMR spectroscopy was used to confirm that tert-butyllithium reacts by a radical disproportionation process, providing lithium atoms that diffuse into the interstitial spaces of the inorganic polymer matrix. The nonreversible reduction potential of tert-butyllithium was estimated at 0.83 V above Li/Li+ by preparation of the reference solid Li0.37WO2. Knowledge of this potential has allowed us to assign tert-butyllithium a relative position within the relative hierarchy of organolithium reagents commonly used in the reductive intercalation of solids.

Original languageEnglish (US)
Pages (from-to)844-849
Number of pages6
JournalChemistry of Materials
Volume6
Issue number6
DOIs
StatePublished - Jun 1 1994
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

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