Journal article

Publication year: 2003

Pages: 4199-4204

Journal: European Journal of Organic Chemistry

Volume number: 2003

Issue number: 21

ISSN: 1434-193X

DOI Link: https://doi.org/10.1002/ejoc.200300201

Publisher: Wiley

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 ortho-cubene 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.

Harvard Citation style: de Visser, S., Filatov, M., Schreiner, P. and Shaik, S. (2003) A REKS assessment of the face-diagonal bond in 1,3-didehydrocubane and a comparison with benzyne biradicals, European Journal of Organic Chemistry, 2003(21), pp. 4199-4204. https://doi.org/10.1002/ejoc.200300201

APA Citation style: de Visser, S., Filatov, M., Schreiner, P., & Shaik, S. (2003). A REKS assessment of the face-diagonal bond in 1,3-didehydrocubane and a comparison with benzyne biradicals. European Journal of Organic Chemistry. 2003(21), 4199-4204. https://doi.org/10.1002/ejoc.200300201