A REKS assessment of the face-diagonal bond in 1,3-didehydrocubane and a comparison with benzyne biradicals

被引：24

作者：

de Visser, SP

Filatov, M

Schreiner, PR

Shaik, S

机构：

[1] Hebrew Univ Jerusalem, Dept Organ Chem, IL-91904 Jerusalem, Israel

[2] Hebrew Univ Jerusalem, Lise Meitner Minerva Ctr Computat Quantum Chem, IL-91904 Jerusalem, Israel

[3] Univ Gothenburg, Dept Theoret Chem, S-41320 Gothenburg, Sweden

[4] Univ Giessen, Inst Organ Chem, D-35392 Giessen, Germany

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2003年 / 2003卷 / 21期

关键词：

density functional calculations; radicals; benzynes; through-space interactions; through-bond interactions;

D O I：

10.1002/ejoc.200300201

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

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. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).

引用

页码：4199 / 4204

页数：6

共 66 条

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