To analyze the evolution of a chemical property along the reaction path, it is necessary to extract all the information from a set of electronic structure computations. However, this process is time-consuming and prone to human error. Here we introduce intrinsic reaction coordinate (IRC)-Analysis, a new extension in Eyringpy, to monitor the evolution of chemical properties along the intrinsic reaction coordinate, including the complete reaction force analysis. IRC-Analysis collects the entire data set for each snapshot of the reaction coordinate, avoiding human error in data capture, and allowing the study of several chemical reactions in seconds. Eyringpy is written in Python, has a simple input format, and no programming skills are required.Python's Matplotlib library is used for plotting the evolution of the properties along the reaction coordinate. This version can analyze the evolution of bond distances, angles, Wiberg bond indices, natural charges, dipole moments, and orbital energies (and related properties).
The mechanisms proposed for the synthesis of diarylamines from diarylsulfinamides are revisited via quantum chemical computations, verifying the 3-exotrig Smiles rearrangement as the most viable pathway. Diarylamine precursors with sterically hindered, electron-rich, or electron-deficient N-aryl rings do not alter the barriers. However, the effects of the substituent on the S-aryl ring of monosubstituted, dimonosubstituted, and trisubstituted diarylsulfinamides can drastically change the rearrangement barriers. Furthermore, our results of rate constants computed at different temperatures show that the temperature rise favors the 3-exo-trig Smiles rearrangement reactions.
Analyzing activation strain, energy decomposition, and reaction force models is crucial for studying chemical reactivity and gaining quantitative insights into the factors that control energy barriers. However, manually preparing and processing the necessary data can be challenging and prone to errors. To address this issue, we introduce SurfinPES, a Python‐based module in Eyringpy that automates data extraction and processing for these analyses. SurfinPES also allows monitoring of the evolution of primitive properties (geometrical and electronic) along the reaction coordinate. The module is user‐friendly with a simple input format, making it accessible to any user in the field of computational chemistry.
Hydroboration of 1,2-dimethylcyclohexene (A) and successive rearrangements yield not only tertiary alkylboranes but also primary and secondary ones. In addition, nontypical anti-addition products are detected, whose formation mechanism is not apparent. Herein, we revisit three mechanisms proposed in the literature: an elimination and readdition, an intramolecular process involving an intermediate π-complex, and an intramolecular migration. According to our computations, the formation of all products starts from the tertiary alkylborane obtained by hydroboration of olefin A. This alkylborane then undergoes a sequence of further retrohydroborations and hydroborations in a syn fashion. Interestingly, the conformational changes on the ring affect these transformations and decide the rearrangement mechanism. Free olefin intermediates are generated during these reactions, which are then rehydroborated from their opposite faces, explaining the formation of anti-addition products. Moreover, the temperature effect on the rearrangement reactions is also analyzed.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.