Circumambulatory migrations of arylazo groups in the systems of pentamethoxycarbonyland pentamethylcyclopentadiene

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Abstract

According to quantum chemical calculations CAM-B3LYP/6-311++G(d,p) intramolecular migrations of arylazo groups in 5-arylazo-1,2,3,4,5-pentamethoxycarbonylcyclopentadienes occur by a dissociative mechanism through the intermediate formation of tight ionic pairs with low energy barriers: Δ E ≠ZPE, benzonitrile, 14.0 (Ar = C6H4NO2-4) and 16.5 [Ar = C6H3(NO2)2-2,4] kcal/mol. In 5-arylazo-1,2,3,4,5-pentamethylcyclopentadienes, 1,5-sigmatropic shifts of arylazo groups occur along the perimeter of the five-membered ring in conformers with the exo position of the azo group relative to the cyclopentadiene ring with significantly higher activation barriers: Δ E ≠ZPE, benzonitrile, 30.3 (Ar = C6H4NO2-4) and 27.5 [Ar = C6H3(NO2)2-2,4] kcal/mol. The calculations are in good agreement with the data for these compounds obtained by us earlier by dynamic NMR.

About the authors

G. A. Dushenko

Institute of Physical and Organic Chemistry of Southern Federal University

Email: gadushenko@sfedu.ru

I. E. Mikhailov

Institute of Physical and Organic Chemistry of Southern Federal University

V. I. Minkin

Institute of Physical and Organic Chemistry of Southern Federal University

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