Barium thiolates and selenolates: Syntheses and structural principles

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Abstract

The synthesis and structural characterization of a family of barium thiolates and selenolates is described. The thiolates were synthesized by metallation of thiols, the selenolates by reductive insertion of the metal into the selenium-selenium bond of diorgano-diselenides. Both reaction sequences were carried out by using barium metal dissolved in ammonia; this afforded barium thiolates and selenolates in good yield and purity. The structural principles displayed in the target compounds span a wide range of solid-state formulations, including monomeric and dimeric species, and separated ion triples, namely [Ba(thf)4(SMes*)2] (1; Mes*=2,4,6-tBu3C6H2), [Ba(thf)4(SeMes*)2] (2), [Ba([18]crown-6)(hmpa)2][(SeMes*)2] (3), the dimeric [{Ba(py)3(thf)(SeTrip)2}2] (4; py=pyridine, Trip=2,4,6-iPr3C6H2), and [Ba([18]crown-6)(SeTrip)2] (5). The full range of association modes is completed by [Ba([18]crown-6)(hmpa)S-Mes*][SMes*] (6) communicated earlier by this group. In the solid state, this compound displays an intermediate ion coordination mode: one anion is bound to the metal, while the second one is unassociated. Together these compounds provide structural information about all three different association modes for alkaline earth metal derivatives. This collection of structural data allows important conclusions about the influence of solvation and ligation on structural trends.

Original languageEnglish (US)
Pages (from-to)4063-4070
Number of pages8
JournalChemistry - A European Journal
Volume6
Issue number22
DOIs
StatePublished - Nov 17 2000

Keywords

  • Barium
  • Chalcogens
  • Coordination chemistry
  • Structure elucidation
  • Synthesis design

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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