Molecular dynamics of the intramolecular 1, 3-dipolar ene reaction of a nitrile oxide and an alkene: non-statistical behavior of a reaction involving a diradical intermediate*. (18th June 2019)

• Record Type: Journal Article
• Authors: Yu, Yanmin; Yang, Zhongyue; Houk, K. N.
• Is Part Of: Molecular physics. Volume 117:Number 9/12(2019)
• Page Start: 1360
• Page End: 1366
• Publication Date: 2019-06-18
• Subjects: Molecular reaction dynamics -- intramolecular 1, 3-dipolar cycloaddition -- carbene-type mechanism -- diradical intermediate; Molecules -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Molécules -- Périodiques; Chimie physique et théorique -- Périodiques; 539.6.05
• DOI: 10.1080/00268976.2018.1549338
• Languages: English
• ISSNs: 0026-8976

Abstract

ABSTRACT: Potential energy surfaces and molecular dynamics of the intramolecular 1, 3-dipolar cycloaddition and ene reaction of a nitrile oxide with an alkene were performed in the gas phase and in dichloromethane with density functional theory. One hundred trajectories were propagated in the gas phase and in dichloromethane, respectively. Twenty percent of the trajectories in the gas phase involve bicyclic intermediate and the mean time gap is 472fs. A dynamically stepwise reaction is observed. In dichloromethane, more reactive trajectories were obtained and the time gap is larger than that in the gas phase. GRAPHICAL ABSTRACT: