Structural and stereochemical nonrigidity of 7-(heptaphenylcycloheptatrienyl) isothiocyanate
- Authors: Dushenko G.A.1, Mikhailov I.E.1, Mikhailova O.I.1, Minyaev R.M.2, Minkin V.I.2
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Affiliations:
- Southern Scientific Center
- Research Institute of Physical and Organic Chemistry
- Issue: Vol 466, No 2 (2016)
- Pages: 35-40
- Section: Chemistry
- URL: https://journals.rcsi.science/0012-5008/article/view/153571
- DOI: https://doi.org/10.1134/S0012500816020051
- ID: 153571
Cite item
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 ΔEZPE≠ = 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.
About the authors
G. A. Dushenko
Southern Scientific Center
Email: mikhail@ipoc.rsu.ru
Russian Federation, ul. Chekhova 41, Rostov-on-Don, 344006
I. E. Mikhailov
Southern Scientific Center
Author for correspondence.
Email: mikhail@ipoc.rsu.ru
Russian Federation, ul. Chekhova 41, Rostov-on-Don, 344006
O. I. Mikhailova
Southern Scientific Center
Email: mikhail@ipoc.rsu.ru
Russian Federation, ul. Chekhova 41, Rostov-on-Don, 344006
R. M. Minyaev
Research Institute of Physical and Organic Chemistry
Email: mikhail@ipoc.rsu.ru
Russian Federation, pr. Stachki 194/2, Rostov-on-Don, 344090
V. I. Minkin
Research Institute of Physical and Organic Chemistry
Email: mikhail@ipoc.rsu.ru
Russian Federation, pr. Stachki 194/2, Rostov-on-Don, 344090