Internal dynamics and optical rotations predicted for Oh- and O-symmetric cubanes

David A. Hrovat, Christine M. Isborn, Bart Kahr, Weston Thatcher Borden

Research output: Contribution to journalArticle

Abstract

(Equation Presented) B3LYP/6-31G(d) calculations find that cubanes, persubstituted with NO2 or BF2 groups, are predicted to undergo near-barrierless, internal disrotations. However, as a consequence of the intrinsically higher energies of eclipsed conformations for threefold than for twofold rotors, the threshold mechanisms for octamethyk octakis(trifluoromethyl)-, octakis(trichloromethyl)-, octakis(tribromomethy|)-, octasilylcubane, and octakis(trichlorosilyl)cubane are calculated to be mono- or conrotation. The cubanes with the larger substituents are predicted to be O-symmetric, resolvable, and thus optically active.

Original languageEnglish (US)
Pages (from-to)4763-4766
Number of pages4
JournalOrganic Letters
Volume10
Issue number21
DOIs
StatePublished - 2008

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Optical rotation
Optical Rotation
cubane
Conformations
Rotors
rotors
thresholds
energy

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Biochemistry

Cite this

Internal dynamics and optical rotations predicted for Oh- and O-symmetric cubanes. / Hrovat, David A.; Isborn, Christine M.; Kahr, Bart; Borden, Weston Thatcher.

In: Organic Letters, Vol. 10, No. 21, 2008, p. 4763-4766.

Research output: Contribution to journalArticle

Hrovat, David A. ; Isborn, Christine M. ; Kahr, Bart ; Borden, Weston Thatcher. / Internal dynamics and optical rotations predicted for Oh- and O-symmetric cubanes. In: Organic Letters. 2008 ; Vol. 10, No. 21. pp. 4763-4766.
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AB - (Equation Presented) B3LYP/6-31G(d) calculations find that cubanes, persubstituted with NO2 or BF2 groups, are predicted to undergo near-barrierless, internal disrotations. However, as a consequence of the intrinsically higher energies of eclipsed conformations for threefold than for twofold rotors, the threshold mechanisms for octamethyk octakis(trifluoromethyl)-, octakis(trichloromethyl)-, octakis(tribromomethy|)-, octasilylcubane, and octakis(trichlorosilyl)cubane are calculated to be mono- or conrotation. The cubanes with the larger substituents are predicted to be O-symmetric, resolvable, and thus optically active.

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