Issue 14, 2022

Violations to the principle of least motion: the shortest path is not always the fastest

Abstract

The reaction between two molecules is usually envisioned as following a least-motion path with both molecules travelling minimum distances to meet each other. However, the reaction path of lowest activation energy is not only determined by practicality but mainly by the orbital symmetry of the involved reactants and the efficiency of their mutual interaction. The term non-least-motion was born to design those reactions in which reactants follow, in their route to products, pathways longer than those intuitively expected. In this review we summarize the theoretical and experimental studies that describe and rationalize reactions following non-least-motion paths, starting with the dimerizations of carbenes and followed by additional processes of these and other reactive species (silylenes, carbynes) such as insertions into single bonds and additions to π-bonds. Other examples involving less reactive partners are also included.

Graphical abstract: Violations to the principle of least motion: the shortest path is not always the fastest

Article information

Article type
Review Article
Submitted
11 2 2022
Accepted
18 3 2022
First published
21 3 2022

Phys. Chem. Chem. Phys., 2022,24, 8064-8075

Violations to the principle of least motion: the shortest path is not always the fastest

M. C. Reis, M. Alajarin and M. Marin-Luna, Phys. Chem. Chem. Phys., 2022, 24, 8064 DOI: 10.1039/D2CP00700B

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