The Laboratory of Theoretical and Computational Chemistry, Science and Engineering College of Chemistry and Biology, Yantai University, Yantai, P R China.
Chemphyschem. 2011 Aug 22;12(12):2289-95. doi: 10.1002/cphc.201100237. Epub 2011 Jun 20.
We designed M(1)⋅⋅⋅C(6)H(5)X⋅⋅⋅HM(2) (M(1) =Li(+), Na(+); X=Cl, Br; M(2) =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(+)⋅⋅⋅C(6)H(5)Br⋅⋅⋅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.
我们设计了 M(1)⋅⋅⋅C(6)H(5)X⋅⋅⋅HM(2)（M(1) =Li(+)、Na(+)；X=Cl、Br；M(2) =Li、Na、BeH、MgH）复合物，以增强卤化物-氢键与阳离子-π 相互作用。主要根据结合距离和相互作用能来估计相互作用强度。结果表明，阳离子-π 相互作用大大增强了卤化物-氢键。三联体中的相互作用能是二联体的两倍到六倍。Li(+)⋅⋅⋅C(6)H(5)Br⋅⋅⋅HNa 复合物中卤键的最大相互作用能为-8.31 kcal·mol(-1)。阳离子、卤化物供体和金属氢化物的性质影响卤键的性质。Li(+)对卤键的增强作用大于 Na(+)。Cl 供体中的卤键的增强效果大于 Br 供体中的卤键。金属氢化物的影响顺序为 HBeH<HMgH<HNa<HLi（对于 Cl 配合物）和 HBeH<HMgH<HLi<HNa（对于 Br 配合物）。大的协同能表明，卤化物-氢键与阳离子-π 相互作用之间存在强烈的相互作用。自然键轨道和能量分解分析表明，静电相互作用在通过阳离子-π 相互作用增强卤键中起主导作用。
