A Computational Study of the Kinetics and Mechanism of the Gas Phase Pyrolysis of Allyl Methyl Amine-Reference-Cited by-同舟云学术

A Computational Study of the Kinetics and Mechanism of the Gas Phase Pyrolysis of Allyl Methyl Amine

Published:2011-02 Issue:1 Volume:36 Page:63-72
ISSN:1468-6783
Container-title:Progress in Reaction Kinetics and Mechanism
language:en
Short-container-title:Progress in Reaction Kinetics and Mechanism

Author:

Izadyar Mohammad¹,Esmaili Effat²,Harati Mohammad³

Affiliation:

1. Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad, I. R. Iran

2. Department of Chemistry, Ganobad University of Payam Noor, Khorasan-e-Razavi, Iran

3. Department of Chemistry and Biochemistry, University of Windsor, Ontario, Canada N9B 3P4

Abstract

A density functional theory (DFT) study has been carried out at the B3LYP/6-31G(d) level on the gas-phase retro-ene reaction of allyl methyl amine (AMN). The results were compared with single point calculations at a high level of the theory, using the G3MP2 method. Two mechanisms for this kind of reaction are possible, one involves a six-membered cyclic transition state (TS) and the other is a multistep, free radical mechanism. Both DFT and high level calculations show that propene and imine formation are in accordance with a concerted cyclic mechanism. Natural bond orbital analysis (NBO) and atoms-in-molecule (AIM) procedures show that the reaction achieves a synchronicity value of 90%. The calculated kinetic parameters for AMN pyrolysis agree with the available experimental results.

Publisher

SAGE Publications

Subject

Physical and Theoretical Chemistry

Link

http://journals.sagepub.com/doi/pdf/10.3184/146867810X12925913885222

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