Structural and stereochemical nonrigidity of 7-(heptaphenylcycloheptatrienyl) isothiocyanate View Full Text


Ontology type: schema:ScholarlyArticle     


Article Info

DATE

2016-02

AUTHORS

G. A. Dushenko, I. E. Mikhailov, O. I. Mikhailova, R. M. Minyaev, V. I. Minkin

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. More... »

PAGES

35-40

Identifiers

URI

http://scigraph.springernature.com/pub.10.1134/s0012500816020051

DOI

http://dx.doi.org/10.1134/s0012500816020051

DIMENSIONS

https://app.dimensions.ai/details/publication/pub.1004639360


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