Unraveling the computed non-least motion pathway for the homodimerization of superchameleonic isocyanides: the peculiar nonsymmetrical (F–NC)2 reactant complex

文献信息

发布日期 2021-07-12

DOI 10.1039/D1CP02674G

影响因子 3.676

作者

Marta Marin-Luna, Mateo Alajarin

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摘要

Isocyanides are commonly qualified as chameleonic compounds because of their reactions with both nucleophiles and electrophiles. In some instances, their chameleonic behavior changes to superchameleonic when they are involved in homodimerization processes, with the two initially identical isocyanide units adopting different roles along the reaction coordinate. We present here a detailed analysis of the computed non-least motion pathway that two isocyanides, the superchameleonic F–NC and, for the sake of comparison, the standard Me–NC, follow when reacting with themselves by comparing the evolution of a series of representative geometrical and electronic parameters along the respective reaction coordinates. This study shows that the two F–NC units are notoriously distinguishable from each other in all the parameters under scrutiny. Furthermore, we envisage that the superchameleonic character of F–NC seems to be most likely due to a minimal electrostatic interaction between the two entities at the earliest stage of the reaction. We also show that MeO–NC, MeS–NC and Me3PN–NC might be postulated as new examples of superchameleonic isocyanides.

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来源期刊

Physical Chemistry Chemical Physics

CiteScore: 5.5

自引率: 10.3%

年发文量: 3036

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.