Pressure-induced formation of molecular B2X4(μ-X)2 (X = Cl, Br, I) species

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DOIResolve DOI: http://doi.org/10.1021/ic2016512
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TypeArticle
Journal titleInorganic Chemistry
Volume50
Issue20
Pages1047210475; # of pages: 4
AbstractBoron(III) halides (BX3, where X = F, Cl, Br, I) at ambient pressure conditions exist as strictly monomeric, trigonal-planar molecules. Using correlated ab initio calculations, the three heavier halides (X = Cl, Br, I) are shown to possess B2X4(μ-X)2 local minima, isostructural with the diborane molecule. The calculated dissociation barrier of the B2I4(μ-I)2 species [≈14 kJ/mol with CCSD(T)/cc-pVTZ] may be high enough to allow cryogenic isolation. The remaining dimer structures are more labile, with dissociation barriers of less than 6 kJ/mol. All three dimer species may be stabilized by application of external pressure. Periodic density functional theory calculations predict a new dimer-based P1̅ solid, which becomes more stable than the P63/m monomer-derived solids at 5 (X = I) to 15 (X = Cl) GPa. Metadynamics simulations suggest that B2X4(μ-X)2-based solids are the kinetically preferred product of pressurization of the P63/m solid.
Publication date
LanguageEnglish
AffiliationNRC Steacie Institute for Molecular Sciences; National Research Council Canada
Peer reviewedYes
NPARC number19734680
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Record identifier7e44e5dc-1c14-467f-854e-652c457990cc
Record created2012-03-29
Record modified2016-05-09
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