Abstract
Decomposition of 2-fluoro-2,3-dihydrophosphinine (1), 2-chloro-2,3-dihydrophosphinine (3), 2-bromo-2,3-dihydrophosphinine (5) to phosphinine was investigated using Molecular orbital and density functional theory. Study on the B3LYP/6-311+G** level of theory revealed that the required energy for the decomposition of compounds 1, 3, and 5 to phosphinine is 30.56 kcal·mol−1, 28.23 kcal·mol−1, and 24.03 kcal·mol−1, respectively. HF/6-311+G**//B3LYP/6-311+G** calculated barrier height for the decomposition of compound 1, 3, and 5 to phosphinine is 57.56 kcal·mol−1, 37.26 kcal·mol−1, and 30.77 kcal·mol−1, respectively. Also, MP2/6-311+G**//B3LYP/6-311+G** results indicated that the barrier height for the decomposition of compound 1, 3, and 5 to phosphinine is 46.59 kcal·mol−1, 47.28 kcal·mol−1, and 42.57 kcal·mol−1, respectively. Natural bond orbital (NBO) population analysis and nuclear independent chemical shift (NICS) results showed that, reactants are non-aromatic but products of elimination reaction are aromatic, C-H and C-X bonds are broken and H-X bond is appear.
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Original Russian Text © 2014 H. Shirani Il Beigi, M. Nikbakht, P. Ghanbar pour.
The text was submitted by the authors in English. Zhurnal Strukturnoi Khimii, Vol. 55, No. 2, pp. 237–242, March–April, 2014.
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Shirani Il Beigi, H., Nikbakht, M. & Ghanbar pour, P. Ab initio study of dehalohydrogenation reaction of 2-halo-2,3-dihydrophosphinine. J Struct Chem 55, 217–222 (2014). https://doi.org/10.1134/S0022476614020048
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DOI: https://doi.org/10.1134/S0022476614020048