On the ring-opening of substituted cyclobutene to benzocyclobutene: analysis of π delocalization, hyperconjugation, and ring strain‡
Literature Information
Paola Nava, Yannick Carissan
The influence of several substituents on the ring-opening elementary step of cyclobutene-like systems is analyzed computationally in detail. We focus on trans-1,2-disiloxycyclobutene-like molecules. Electronic effects (hyperconjugation and π delocalization) and geometrical constraints are decoupled and allow for an instructive analysis. It is found that the energy difference between closed and open forms is dictated mainly by the electronic structure of the open form, in which the rotation along the resulting simple C–C bond drives the electronic delocalization. Our calculations led us to quantify effects that determine the energy difference in the special case of disubstituted benzocyclobutene with respect to the disubstituted o-xylylene (aromaticity, π delocalization, ring strain). The relevant role of the siloxy-substituents is rationalized by an analysis of the molecular orbital interaction in an original manner. Finally, calculations are presented and show that the PBE0 functional must be preferred to the popular B3LYP functional for computations on substituted cyclobutene-like rings.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










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