Open AccessPotential Energy Surfaces of Vinylogous Wolff Rearrangement: NBO Analysis and Molecular Dynamic Simulation
Author(s) -
Nahzomi Hossein Taherpour,
Divsar Faten
Publication year - 2021
Publication title -
chemistryopen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.644
H-Index - 29
ISSN - 2191-1363
DOI - 10.1002/open.202100049
Subject(s) - diradical , natural bond orbital , transition state , chemistry , potential energy , computational chemistry , potential energy surface , wolff rearrangement , chemical physics , ab initio , atomic physics , physics , density functional theory , organic chemistry , ketene , singlet state , excited state , catalysis
The potential energy surfaces of the Vinylogous Wolff Rearrangement, an alternative process for the Wolff Rearrangement that takes place β,γ‐unsaturated diazoketones have been fully explored employing M062X model chemistry and in a complementary task by means of the CASSCF method. The NBO analysis has been invoked to reveal the alternations of orbital occupancies and their stabilization energies through some of the critical structures located on the pathways. The calculations establish a two steps process for each pathway involving a second higher energy transition state that seems likely to be the rate determining step in agreement with experimental results. Energy analysis indicates more feasibility of the pathway including diradical intermediate. The most striking feature of the study concerns the finding out a transition state providing a channel in between two pathways through interconversion of the two keys bicyclo[2.1.0]pentanone and diradical intermediates.