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

doi:10.1002/ejoc.200300201

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

Research output: Contribution to journal › Article › peer-review

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. © Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

Original language	English
Pages (from-to)	4199-4204
Number of pages	5
Journal	European Journal of Organic Chemistry
Issue number	21
DOIs	https://doi.org/10.1002/ejoc.200300201
Publication status	Published - 31 Oct 2003

Keywords

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

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@article{7c34fd98f5884b16a7e78565fd434119,

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

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. {\textcopyright} Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.",

keywords = "Benzynes, Density functional calculations, Radicals, Through-bond interactions, Through-space interactions",

author = "{De Visser}, {Sam P.} and Michael Filatov and Schreiner, {Peter R.} and Sason Shaik",

year = "2003",

month = oct,

day = "31",

doi = "10.1002/ejoc.200300201",

language = "English",

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journal = "European Journal of Organic Chemistry",

issn = "1099-0690",

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T1 - A REKS Assessment of the Face-Diagonal Bond in 1,3-Didehydrocubane and a Comparison with Benzyne Biradicals

AU - De Visser, Sam P.

AU - Filatov, Michael

AU - Schreiner, Peter R.

AU - Shaik, Sason

PY - 2003/10/31

Y1 - 2003/10/31

N2 - 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. © Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

AB - 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. © Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

KW - Benzynes

KW - Density functional calculations

KW - Radicals

KW - Through-bond interactions

KW - Through-space interactions

U2 - 10.1002/ejoc.200300201

DO - 10.1002/ejoc.200300201

M3 - Article

SN - 1099-0690

SP - 4199

EP - 4204

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

IS - 21

ER -

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

Abstract

Keywords

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