Icosahedral carborane superacids and their conjugate bases comprising H, F, Cl, and CN substituents: a theoretical investigation of monomeric and dimeric cages

Jakub Brzeski , Marcin Czapla , Piotr Skurski

Abstract

Theoretical investigation of the H(CHB11 X11 ) (X=H, F, Cl, CN), H(CHB11 Xn Y11-n ) (X,Y=F, Cl; n=1,5), and dimeric (H(CHB11 X11 ))2 (X=F, Cl) carborane superacids performed at the B3LYP/6-311++G(d,p) theory level revealed the similarity of their equilibrium structures and the possibility of nearly barrierless hydrogen atom migration among the substituents attached to one side of the icosahedral CB11 cage. The vertical electron detachment energies predicted at the OVGF/6-311++G(3df,2pd) theory level for the conjugate bases (CHB11 X11 )- were found to span the 5.82-9.00 ev range. The acid strengths (manifested by the Gibbs free deprotonation energies spanning the 213-266 kcal/mol range) predicted for the icosahedral H(CHB11 X11 ) carborane systems confirm their superacidic properties which might be increased even further by the attachment of the second carborane H(CHB11 X11 ) unit that leads to a dimeric structure mimicking a part of an experimentally observed H-bridged polymeric chain. The Gibbs free deprotonation energy of the dimeric (H(CHB11 Cl11 ))2 acid was predicted to be smaller by 17 kcal/mol than that of the corresponding monomeric H(CHB11 Cl11) acid.
Author Jakub Brzeski (FCh / KChBionieorg. / LII)
Jakub Brzeski,,
- Laboratory of Intermolecular Interactions
, Marcin Czapla (FCh / DTCh / LQCh)
Marcin Czapla,,
- Laboratory of Quantum Chemistry
, Piotr Skurski (FCh / DTCh / LQCh)
Piotr Skurski,,
- Laboratory of Quantum Chemistry
Journal seriesChemPlusChem, ISSN 2192-6506, (N/A 100 pkt)
Issue year2020
Vol85
No2
Pages312-318
Publication size in sheets0.5
Keywords in Englishcarboranes, density functional theory, H-bridgedchains, proton mobility, super acidics
ASJC Classification1600 General Chemistry
DOIDOI:10.1002/cplu.202000007
URL https://onlinelibrary.wiley.com/doi/epdf/10.1002/cplu.202000007
Languageen angielski
Score (nominal)100
Score sourcejournalList
ScoreMinisterial score = 100.0, 14-05-2020, ArticleFromJournal
Publication indicators WoS Citations = 0; Scopus SNIP (Source Normalised Impact per Paper): 2018 = 0.604; WoS Impact Factor: 2018 = 3.441 (2) - 2018=2.869 (5)
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