A REKS Assessment of the Face-Diagonal Bond in 1,3-Didehydrocubane and a Comparison with Benzyne Biradicals

Sam P. De Visser, Michael Filatov, Peter R. Schreiner*, Sason Shaik

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

35 Scopus citations

Abstract

The three isomeric cubane biradicals were studied using spin-restricted ensemble-referenced Kohn-Sham (REKS) density functional calculations at the B3LYP/6-31G(d) level of theory. The most stable biradical was found to be orthocubene with the meta-cubene and para-cubene biradicals 4.7 kcal mol -1 and 17.8 kcal mol-1 higher in energy, respectively. The singlet ground states are well separated from their lowest lying triplet states. These singlet-triplet energy differences mostly originate from through-space interactions for the ortho and meta isomers, whereas these interactions are rather weak for the para isomer. In contrast to para-benzyne, which was also considered for comparison with an unsaturated system, the singlet-triplet energy gap remains large in para-cubadiyl, mainly as a result of its much stronger through-bond interactions.

Original languageEnglish
Pages (from-to)4199-4204
Number of pages6
JournalEuropean Journal of Organic Chemistry
Issue number21
DOIs
StatePublished - 31 Oct 2003

Keywords

  • Benzynes
  • Density functional calculations
  • Radicals
  • Through-bond interactions
  • Through-space interactions

Fingerprint

Dive into the research topics of 'A REKS Assessment of the Face-Diagonal Bond in 1,3-Didehydrocubane and a Comparison with Benzyne Biradicals'. Together they form a unique fingerprint.

Cite this