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Ab initio and DFT investigation of electrophilic addition reaction of bromine to endo,endo-tetracyclo[4.2.1.13,6.02,7]dodeca-4,9-diene

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Abstract

Full geometric optimization of endo,endo-tetracyclo[4.2.1.13,6.02,7]dodeca-4,9-diene (TTDD) has been carried out by ab initio and DFT/B3LYP methods and the structure of the molecule investigated. The double bonds of TTDD molecule are endo pyramidalized. The structure of π-orbitals and their mutual interactions for TTDD molecule were investigated. The cationic intermediates and products obtained as a result of the addition reaction have been studied using the HF/6-311G(d), HF/6-311G(d,p) and B3LYP/6-311G(d) methods. The bridged bromonium cation isomerized into the more stable N- and U-type cations and the difference between the stability of these cations is small. The N- and U-type reaction products are obtained as a result of the reaction, which takes place via the cations in question. The stability of exo, exo and exo, endo isomers of N-type product are nearly the same and the formation of both isomers is feasible. The U-type product basically formed from the exo, exo-isomer. Although the U-type cation was 0.68 kcal mol−1 more stable than the N-type cation, the U-type product was 4.79 kcal mol−1 less stable than the N-type product.

The energy diagram of TTDD–Br2 system (kcal mol−1)(MP2/6-311G*//HF/6-311G*)

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Scheme 1
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  1. Department of Chemistry, Karadeniz Technical University, 61080, Trabzon, Turkey

    Rza Abbasoglu

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  1. Rza Abbasoglu
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Correspondence to Rza Abbasoglu.

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Abbasoglu, R. Ab initio and DFT investigation of electrophilic addition reaction of bromine to endo,endo-tetracyclo[4.2.1.13,6.02,7]dodeca-4,9-diene. J Mol Model 13, 425–430 (2007). https://doi.org/10.1007/s00894-006-0161-8

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