The Prominent Enhancing Effect of the Cation–π Interaction on the Halogen–Hydride Halogen Bond in M1⋅⋅⋅C6H5X⋅⋅⋅HM2 |
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Authors: | Ran Li Prof Dr Qingzhong Li Prof Dr Jianbo Cheng Zhenbo Liu Prof Dr Wenzuo Li |
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Institution: | The Laboratory of Theoretical and Computational Chemistry, Science and Engineering College of Chemistry and Biology, Yantai University, Yantai 264005 (P. R. China), Fax. (+086) 535 6902063 |
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Abstract: | We designed M1???C6H5X???HM2 (M1=Li+, Na+; X=Cl, Br; M2=Li, Na, BeH, MgH) complexes to enhance halogen–hydride halogen bonding with a cation–π interaction. The interaction strength has been estimated mainly in terms of the binding distance and the interaction energy. The results show that halogen–hydride halogen bonding is strengthened greatly by a cation–π interaction. The interaction energy in the triads is two to six times as much as that in the dyads. The largest interaction energy is ?8.31 kcal mol?1 for the halogen bond in the Li+???C6H5Br???HNa complex. The nature of the cation, the halogen donor, and the metal hydride influence the nature of the halogen bond. The enhancement effect of Li+ on the halogen bond is larger than that of Na+. The halogen bond in the Cl donor has a greater enhancement than that in the Br one. The metal hydride imposes its effect in the order HBeH<HMgH<HNa<HLi for the Cl complex and HBeH<HMgH<HLi<HNa for the Br complex. The large cooperative energy indicates that there is a strong interplay between the halogen–hydride halogen bonding and the cation–π interaction. Natural bond orbital and energy decomposition analyses indicate that the electrostatic interaction plays a dominate role in enhancing halogen bonding by a cation–π interaction. |
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Keywords: | cation– pi interactions computational chemistry cooperative effects energy decomposition halogen bonding |
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