Regular/abnormal variation in the strength and nature of the halogen bond between H2Te and the dihalogens: Prominent effect of methyl substituents |
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| Authors: | Ruijing Wang Ziyi Cheng Qingzhong Li Sean AC McDowell |
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| Institution: | 1. The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, Yantai, 264005 China;2. Institute of Functional Materials and Molecular Imaging, Key Laboratory of Emergency and Trauma, Ministry of Education, College of Emergency and Trauma, Hainan Medical University, Haikou, 571199 China;3. Department of Biological and Chemical Sciences, The University of the West Indies, Cave Hill, Campus, Barbados |
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| Abstract: | The halogen-bonded complexes between H2Te/Me2Te and the dihalogen molecules XY (XY = F2, Cl2, Br2, I2, ClF, ClBr, BrF, BrCl, BrI, IF, ICl, IBr) have been studied to investigate the dependence of its strength and nature on the halogen donor X and its adjoining atom Y, as well as the methyl groups in the electron donor. The interaction energy varies between −1.7 and − 43.5 kcal/mol, indicating that the Te atom in H2Te/Me2Te has a strong affinity for the dihalogen molecules. For the H2Te-XY complex, the halogen bond is stronger for the heavier halogen donor X atom and the strong electron-withdrawing group Y. However, for Me2Te-XY, the halogen bond is stronger for the lighter halogen donor X atom. The H2Te/Me2Te-F2 complex has the largest interaction energy, although the σ-hole on F2 is the smallest in magnitude. In most of the complexes, the electrostatic and polarization contributions to the binding strength are similar in magnitude. However, for H2Te/Me2Te-F2, the polarization contribution is much larger than the electrostatic contribution, with a significant contribution from charge transfer. |
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| Keywords: | AIM halogen bonding MEP methyl substituents NBO |
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