Molecular E(CN) sub(3) (E=Sb, Bi) Species Synthesized from Ionic Liquids as Solvates

The heavy pnictogen tricyanides, E(CN) sub(3) (E=Sb, Bi), were synthesized from EF sub(3) and Me sub(3)SiCN in ionic liquids, for example, 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([BMIm][OTf]), which prevents the oligomerization of the molecular E(CN) sub(3) species by formation of [BM...

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Published inChemistry : a European journal Vol. 22; no. 45; pp. 16012 - 16016
Main Authors Arlt, Soren, Harloff, Jorg, Schulz, Axel, Stoffers, Alrik, Villinger, Alexander
Format Journal Article
LanguageEnglish
Published 01.11.2016
Subjects
Adducts
Formations
Ionic liquids
Oligomerization
Polymerization
Recrystallization
Solvents
Synthesis (chemistry)
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Summary:The heavy pnictogen tricyanides, E(CN) sub(3) (E=Sb, Bi), were synthesized from EF sub(3) and Me sub(3)SiCN in ionic liquids, for example, 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([BMIm][OTf]), which prevents the oligomerization of the molecular E(CN) sub(3) species by formation of [BMIm][E(CN) sub(3)(OTf)] salts in solution. Recrystallization of [BMIm][E(CN) sub(3)(OTf)] from THF led to the isolation and full characterization of the molecular species E(CN) sub(3)2THF. Ionic liquid makes it molecular! Labile E(CN) sub(3) molecules were generated and stabilized in ionic liquids (IL) as molecular entities of the type [E(CN) sub(3)X sub(n)] super(n-) (X super(-)=counterion of the IL), thereby preventing E(CN) sub(3) from polymerization. Isolation of molecular adducts of E(CN) sub(3) was achieved after treating [E(CN) sub(3)X sub(n)] super(n-) ions with polar organic solvents, such as THF (see scheme).
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ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201603849