Enhancement of the Tetrel Bond by the Effects of Substituents,Cooperativity, and Electric Field: Transition from Noncovalent to Covalent Bond |
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| Authors: | Dr Na Liu Xiaoying Xie Qingzhong Li Prof Steve Scheiner |
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| Institution: | 1. Laboratory of Theoretical and Computational Chemistry and, School of Chemistry and Chemical Engineering, Yantai University, Yantai, 264005 China
These authors contributed equally to this work.;2. Laboratory of Theoretical and Computational Chemistry and, School of Chemistry and Chemical Engineering, Yantai University, Yantai, 264005 China;3. Department of Chemistry and Biochemistry, Utah State University, Logan, UT 84322–0300 USA |
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| Abstract: | The T⋅⋅⋅N tetrel bond (TB) formed between TX3OH (T=C, Si, Ge; X=H, F) and the Lewis base N≡CM (M=H, Li, Na) is studied by ab initio calculations at the MP2/aug-cc-pVTZ level. Complexes involving TH3OH contain a conventional TB with interaction energy less than 10 kcal/mol. This bond is substantially strengthened, approaching 35 kcal/mol and covalent character, when fluorosubstituted TF3OH is combined with NCLi or NCNa. Along with this enhanced binding comes a near equalization of the TB T⋅⋅⋅N and the internal T−O bond lengths, and the associated structure acquires a trigonal bipyramidal shape, despite a high internal deformation energy. This structural transformation becomes more complete, and the TB is further strengthened upon adding an electron acceptor BeCl2 to the Lewis acid and a base to the NCM unit. This same TB strengthening can be accomplished also by imposition of an external electric field. |
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| Keywords: | Be-bond AIM electric field tetrel bond energy decomposition |
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