高等学校化学学报 ›› 1997, Vol. 18 ›› Issue (11): 1833.

• 论文 • 上一篇    下一篇

异丙基膦酸单烷基酯萃取剂的量子化学研究

张绍文1, 沈剑韵1, 冯文林2, 王淀佐1   

  1. 1. 北京有色金属研究总院冶金物化中心, 北京 100088;
    2. 北京师范大学化学系, 北京 100875
  • 收稿日期:1996-08-01 出版日期:1997-11-24 发布日期:1997-11-24
  • 通讯作者: 张绍文, 男, 34岁, 博士, 讲师
  • 作者简介:张绍文, 男, 34岁, 博士, 讲师
  • 基金资助:

    吉林大学理论与计算化学国家重点实验室资助

Quantum Chemistry Study on the Isopropylphosphonate Rare Earth Extractants

ZHANG Shao-Wen1, SHEN Jian-Yun1, FENG Wen-Lin2, WANG Dian-Zuo1   

  1. 1. General Research Institute for Non-ferrous Metals of Beijing, Beijing 100088;
    2. Chemistry Department of Beijing Normal University, Beijing 100875
  • Received:1996-08-01 Online:1997-11-24 Published:1997-11-24

摘要: 用分子力学、分子动力学及半经验量子化学方法研究了异丙基膦酸单烷基酯系列稀土萃取剂的空间结构和电子结构.结果表明,烷氧基上的取代基对空间位阻的影响比主碳链大.与稀土原子配位的磷酰氧原子在HOMO中的贡献较大,而LUMO轨道则主要由非配位原子的轨道组成.萃取剂中磷原子、磷酸氧原子以及羟基中氧原子上的电荷分布均随结构的变化呈规律性变化.磷原子和磷酸氧原子上的电荷分布与萃取剂的pKa值呈线性关系.

关键词: 异两基膦酸单烷基酯, 萃取剂, 分子动力学, 半经验量子化学方法

Abstract: Molecular dynamics method and semi-empirical quantum chemistry method havebeen used to study the geometric and electronic structure of seven isopropylphosphonate rareearth extractants.The geometry of each extractant was first obtained through MolecularAnnealing; then basd on the most stable structure optimized by Molecular Annealing, thegeometry was further optimized by using PM3 method.The results show that thesubstituent on the alkoxy group exhibits a stronger space obstacle effect than the main chain.The phosphonyl oxygen atom, which is the coordinate atom with the rare earth atom, hasthe largest component in HOMOorbitals.The LUMOorbitals consist of the contribution ofnon-coordinate orbitals.This results indicate that the HOMOof isopropylphosphonate mightplay an important role in the complex compound.The calculated atomic charges ofphosphorus atom, phosphoryl oxygen atom, hydroxy oxygen atom and hydroxy hydrogen atom varyregularly with the change of the size and position of substituents.We have found that thecharges of hydroxy oxygen atom and phosphorus atom have a linear relationship with theacid dissociation constants (pKa) of the extractants.

Key words: Isopropylphosphonate, Extractants, Molecular dynamics, Semi-empirical quantum chemistry method

中图分类号: 

TrendMD: