A σ-hole interaction with radical species as electron donors: does single-electron tetrel bonding exist?

Literature Information

Publication Date 2014-04-17
DOI 10.1039/C4CP01209G
Impact Factor 3.676
Authors

Qingzhong Li, Xin Guo, Xin Yang, Wenzuo Li, Jianbo Cheng, Hai-Bei Li


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Abstract

A single-electron tetrel bond was predicted and characterized in FXH3⋯CH3 (X = C, Si, Ge, and Sn) complexes by performing quantum chemical calculations, where the methyl radical acts as the Lewis base and the σ-hole on the X atom in FXH3 as the Lewis acid. The interaction between the methyl radical and FXH3 is characterized by a red shift of F–X stretching frequency. The strength of the tetrel bond becomes stronger by not only increasing the atomic number of the central atom X (X = C, Si, Ge, and Sn) but also by enhancing the electron-withdrawing ability of substituents in the Lewis acid. The energy decomposition analysis highlights the importance of the electrostatic interaction in the formation of the tetrel bond, although the dispersion part is also non-negligible for the weak tetrel bond. There is a competition between the formation of single-electron tetrel bonds and hydrogen bonds for the complexes composed of the methyl radical and CNCH3 or NCCH3. Furthermore, the single-electron tetrel bond exhibits the cooperative effect not only with the hydrogen bond in the complex of NCH⋯NCCH3⋯CH3, but also with the conventional tetrel bond in NCCH3⋯NCCH3⋯CH3.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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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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