Acta Chimica Sinica ›› 2012, Vol. 70 ›› Issue (12): 1347-1354.DOI: 10.6023/A1111211 Previous Articles     Next Articles

Special Topic

碱(土)金属离子与2-(3′-羟基-2′-吡啶基)苯并噁唑阳离子-π 复合物及其分子内质子转移过程的理论研究

易平贵, 刘峥军, 汪朝旭, 侯博, 于贤勇, 李筱芳   

  1. 湖南科技大学化学化工学院 理论化学与分子模拟省部共建教育部重点实验室 分子构效关系湖南省普通高等学校重点实验室 湘潭 411201
  • 投稿日期:2011-11-21 修回日期:2012-04-20 发布日期:2012-04-20
  • 通讯作者: 易平贵
  • 基金资助:

    国家自然科学基金(Nos. 21172066, 20772027)湖南省自然科学基金(Nos. 10JJ4011, 11JJ2007)和湖南省高校创新平台开放基金(No. 09K081).

Alkali (Alkali Earth) Metal Ions with 2-(3'-Hydroxy-2'-pyridyl)benzoxazole Cation-π Complexes and Its Intramolecular Proton Transfer Process: A Theoretical Investigation

Yi Pinggui, Liu Zhengjun, Wang Zhaoxu, Hou Bo, Yu Xianyong, Li Xiaofang   

  1. Key Laboratory of Theoretical Chemistry and Molecular Simulation of Ministry of Education, Hunan Province College Key Laboratory of QSAR/QSPR, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201
  • Received:2011-11-21 Revised:2012-04-20 Published:2012-04-20
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21172066, 20772027), Hunan Provincial Natural Science Foundation of China (Nos.10JJ4011, 11JJ2007), Scientific Research Fund of Hunan Provincial Education Department (No. 09K081).

The structures of 2-(3'-hydroxy-2'-pyridyl)benzoxazole (HPyBO) with alkali (or alkaline earth) metal ions (Li+, Na+, K+, Be2+, Mg2+ and Ca2+) were fully optimized at the 6-311++G(d,p) level by using B3LYP density functional theory and the binding energies were calculated at the same level. The result shows that the cation-π interaction between alkali (or alkaline earth) metal ions and HPyBO complexes are very strong, some of the interactions are even comparable to chemical bonding. The relative energies show that cation-π interaction can change the energy barrier of intramolecular proton transfer. When considering the solvent effect of water, the relative energies of isomers and the energy barrier of intramolecular proton transfer are changed to some extent. In addition, the properties at the BCPs (bond critical points) of intramolecular hydrogen bond in the complexes are also discussed.

Key words: density functional theory (DFT), cation-π interaction, intramolecular proton transfer, natural bond orbital (NBO), atoms in molecules (AIM)