Revisiting the Rearrangement of Dewar Thiophenes
Scuola Normale Superiore, Classe di Scienze, Piazza dei Cavalieri 7, 56126 Pisa, Italy
Facultad de Ciencias Naturales y Matemáticas, Universidad de Ibagué, Carrera 22 Calle 67, Ibagué, Colombia
Departamento de Física Aplicada, Centro de Investigación y de Estudios Avanzados, Unidad Mérida. Km 6 Antigua Carretera a Progreso, Apdo. Postal 73, Cordemex, 97310 Mérida, Mexico
Departamento de Ciencias Químicas, Facultad de Ciencias Exactas, Universidad Andres Bello, Av. República 275, Santiago, Chile
Instituto de Química, Universidad de Antioquia UdeA, Calle 70 No. 52-21, Medellín, Antioquia, Colombia
Authors to whom correspondence should be addressed.
Molecules 2020, 25(2), 284; https://doi.org/10.3390/molecules25020284
Received: 6 December 2019 / Revised: 29 December 2019 / Accepted: 2 January 2020 / Published: 10 January 2020
(This article belongs to the Special Issue Modern Computational Methods for Chemical Bonding and Reactivity)
The mechanism for the walk rearrangement in Dewar thiophenes has been clarified theoretically by studying the evolution of chemical bonds along the intrinsic reaction coordinates. Substituent effects on the overall mechanism are assessed by using combinations of the ring (R = H, CF3) and traveling (X = S, S = O, and CH2) groups. The origins of fluxionality in the S–oxide of perfluorotetramethyl Dewar thiophene are uncovered in this work. Dewar rearrangements are chemical processes that occur with a high degree of synchronicity. These changes are directly related to the activation energy.