Antiaromaticity of Cycloheptatrienyl Anions: Structure, Acidity, and Magnetic Properties

Author:

Salikov Rinat F.12ORCID,Belyy Alexander Y.1,Ilyushchenko Matvey K.1,Platonov Dmitry N.1,Sokolova Alena D.1,Tomilov Yury V.1ORCID

Affiliation:

1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences 47 Leninsky prosp. Moscow 119991 Russian Federation

2. Department of Chemistry Higher School of Economics National Research University Moscow 101000 Russian Federation

Abstract

AbstractInvestigations of the nature and degree of antiaromaticity of cycloheptatrienyl anion derivatives using both experimental and computational tools are presented. The ground state of cycloheptatrienyl anion in the gas phase is triplet, planar and Baird‐aromatic. In DMSO, it assumes a singlet distorted allylic form with a paratropic ring current. The other derivatives in both phases assume either allylic or diallylic conformations depending on the substituent pattern. A combination of experimental and computational methods was used to determine the pKa values of 16 derivatives in DMSO, which ranged from 36 to −10.7. We revealed that the stronger stabilization of the anionic system, which correlates with acidity, does not necessarily imply a lower degree of antiaromaticity in terms of magnetic properties. Conversely, the substitution pattern first affects the geometry of the ring through the bulkiness of the substituents and their better conjugation with a more distorted system. Consequently, the distortion reduces the cyclic conjugation in the π‐system and thereby decreases the paratropic current in a magnetic field, which manifests itself as a decrease in the NICS. The triplet‐state geometries and magnetic properties are nearly independent on the substitution pattern, which is typical for simple aromatic systems.

Funder

Russian Science Foundation

Publisher

Wiley

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