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- Publisher
- Springer Journals
- Copyright
- Copyright © 2016 by Pleiades Publishing, Ltd.
- Subject
- Chemistry; Chemistry/Food Science, general; Industrial Chemistry/Chemical Engineering
- ISSN
- 0012-5008
- eISSN
- 1608-3113
- DOI
- 10.1134/S0012500816020051
- Publisher site
- See Article on Publisher Site
Abstract
By means of DFT B3LYP/6-31G(d, p) calculations of 7-(heptaphenylcycloheptatrienyl) isothiocyanate, the dissociation–recombination mechanism for intramolecular migrations of the isothiocyanato group has been revealed, and the structure of the transition state preceding the formation of a tight ion pair has been found for the first time. According to calculations, the high activation barrier for displacements of the isothiocyanato group ΔE ZPE ≠ = 21.3 kcal/mol is related to the stable conformation of the molecule with the equatorial–NCS group and the orthogonally located phenyl substituent in the axial position. The rearrangement of the molecule to the form favorable for migrations of the–NCS group involves the inversion of the seven-membered ring accompanied by rotation of the phenyl group.
Journal
Doklady Chemistry – Springer Journals
Published: Apr 1, 2016