高等学校化学学报

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (11): 2241.doi: 10.7503/cjcu20150636

• 物理化学 • 上一篇    下一篇

含BF配体的锇羰基化合物Os(BF)(CO)n(n=4, 3)和Os2(BF)2(CO)n(n=7, 6, 5, 4)稳定性的理论研究

彭彬1, 罗琼1, 李楠2, 张秀辉2, 李前树3()   

  1. 1. 华南师范大学量子化学计算研究中心, 环境理论化学教育部重点实验室, 广州 510631
    2. 北京理工大学理学院, 爆炸科学与技术国家重点实验室, 北京 100081
    3. 陕西师范大学化学化工学院, 应用表面与胶体化学教育部重点实验室, 西安 710139
  • 收稿日期:2015-08-11 出版日期:2015-11-10 发布日期:2015-10-23
  • 作者简介:联系人简介: 李前树, 男, 博士, 教授, 博士生导师, 主要从事量子化学基础理论、 非线性化学、 分子结构和化学键、 原子簇的结构和结构规则等研究. E-mail:qsli@scnu.edu.cn
  • 基金资助:
    国家自然科学基金(批准号: 21273082)资助

Theoretical Studies on Mononuclear and Binuclear Osmium Fluoroborylene Carbonyls Os(BF)(CO)n(n=4, 3) and Os2(BF)2(CO)n(n=7, 6, 5, 4)†

PENG Bin1, LUO Qiong1, LI Nan2, ZHANG Xiuhui2, LI Qianshu3,*()   

  1. 1. Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, Center for Computational Quantum Chemistry, South China Normal University, Guangzhou 510006, China
    2. State Key Laboratory of Explosion Science and Technology,School of Chemistry, Beijing Institute of Technology, Beijing 100081, China
    3. Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education,School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an, 710139, China
  • Received:2015-08-11 Online:2015-11-10 Published:2015-10-23
  • Contact: LI Qianshu E-mail:qsli@scnu.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(No.21273082)

RichHTML

PDF (PC)

摘要：

采用MPW1PW91和BP86 2种密度泛函方法对中性单核锇羰基化合物Os(BF)(CO)n(n=4, 3)及双核锇羰基化合物Os2(BF)2(CO)n(n=7, 6, 5, 4)进行理论计算研究, 优化得到22个低能异构体. 研究发现, 单核配位饱和Os(BF)(CO)4 的能量最低的异构体对称性为C2v, 其BF基团在三角双锥赤道面上. 该异构体失去1个赤道面上的CO可得到Os(BF)(CO)3的能量最低异构体. 单核Os(BF)(CO)n(n=4, 3)的能量最低异构体的BF基团都位于配体三角双锥及缺顶点结构的赤道面上. 配位饱和双核Os2(BF)2(CO)7有4个能量接近的异构体, 其中能量最低的异构体结构中含有2个呈蝶形的桥配位BF基团. 配位不饱和的Os2(BF)2(CO)6 的2个能量接近的异构体结构相似, 2个桥配位BF基团与2个Os原子构成平行四边形结构单元. 配位不饱和的Os2(BF)2(CO)5和Os2(BF)2(CO)4的能量最低异构体都含有由2个桥配位BF基团与2个Os原子构成的平行四边形结构单元. 双核Os2(BF)2(CO)n(n=7, 6, 5, 4) 能量最低异构体的BF基团都以桥配位形式和Os原子相连. 离解能研究表明, 单核配位饱和的Os(BF)(CO)4具有一定的热力学稳定性. 双核的Os2(BF)2(CO)n(n=7, 6)失去1个CO或者分裂为单核的Os(BF)(CO)4或Os(BF)(CO)3 所需能量较高, 表明其具有一定的热力学稳定性.

关键词: 密度泛函理论, BF配体, 锇羰基化合物, 理论研究

Abstract:

Mononuclear and binuclear osmium fluoroborylene carbonyls Os(BF)(CO)n(n=4,3) and Os2(BF)2(CO)n(n=7, 6, 5, 4) were investigated using MPW1PW91 and BP86 density functional theories. Twenty two isomers were obtained. For Os(BF)(CO)4, the lowest-energy structure 14-1 is a singlet C2v symmetrical trigonal bipyramid. The lowest energy structures for Os(BF)(CO)3 are derived from the trigonal bipyramidal Os(BF)(CO)4 structures by removal of a CO group. Four low energy isomers are predicted to be close in energy for Os2(BF)2(CO)7, the lowest-energy isomer, 27-1, has butterfly structure containing two bridging BF groups. For Os2(BF)2(CO)6. Two isomers, 26-1 and 26-2, are predicted to be nearly degenerated in energy. Both 26-1 and 26-2 are predicted to have two bridging BF groups. The global minimum isomer of Os2(BF)2(CO)5 and Os2(BF)2(CO)4 are similar to 26-1 with two BF groups bridging to two Os atoms. It seems that Os2(BF)2(CO)n(n=7, 6, 5, 4) are favored to form structures containing bridging fluoroborylene groups. The study of dissociation energy shows that the CO dissociation energy and dissociation energy of Os2(BF)2(CO)n(n=7, 6) into the mononuclear fragments Os(BF)(CO)4 or Os(BF)(CO)3 are large, suggesting those isomers are quite thermodynamically favorable.

Key words: Density functional theory(DFT), BF ligand, Osimum carbonyl, Theoretical study

中图分类号: 

TrendMD: