N -Phenyl-1-methyl-6-methylenecyclohexa-2,4-dienylmethanimine retro cheletropic-ene reaction, a theoretical kinetic study

Structural and kinetic aspects of the retro-cheletropic ene reactions of N-phenyl-1-methyl-6-methylenecyclohexa-2,4-dienylmethanimine (R) and its deuterated derivative were investigated using a variety of computational methods. Theoretical calculations were carried out with DFT methods at the B3LYP...

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Bibliographic Details
Published in:Progress in reaction kinetics and mechanism 2013-01, Vol.38 (4), p.408-416
Main Author: Izadyar, M
Format: Article
Language:English
Subjects:
Activation
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Summary:Structural and kinetic aspects of the retro-cheletropic ene reactions of N-phenyl-1-methyl-6-methylenecyclohexa-2,4-dienylmethanimine (R) and its deuterated derivative were investigated using a variety of computational methods. Theoretical calculations were carried out with DFT methods at the B3LYP and M06 levels of theory, using the 6-311++G(d,p) basis set. Vibrational frequency analysis confirmed the stationary states including the transition state (TSs) structures. The mechanistic studies on the retro-cheletropic ene processes rejected the stepwise mechanism and confirmed a five-membered cyclic TS for the reaction. The conversion of the reactant to the products proceeds through an asynchronous concerted mechanism. Theoretical calculations indicate that the reaction displays a primary kinetic isotope effect of 8.75 at 417 K. Calculated activation parameters, especially M06 results, are in go o d agreement with the experimental data. The natures of bond making and breaking during the reactions have been investigated using the concepts of donor-acceptor, electron charge density and Laplacian in NBO and AIM methods, respectively.
ISSN:1468-6783
1471-406X
DOI:10.3184/146867813X13744829848080