物理化学学报 >> 2012, Vol. 28 >> Issue (07): 1658-1664.doi: 10.3866/PKU.WHXB201205101

理论与计算化学 上一篇    下一篇

取代基对咔咯锰(V)-氧配合物Mn―O的成键影响

何婧1, 徐志广1, 曾允秀1, 许旋1, 喻兰2, 王琦2, 刘海洋2   

  1. 1. 华南师范大学化学与环境学院, 教育部环境理论化学重点实验室, 广州 510006;
    2. 华南理工大学化学系, 广州 510641
  • 收稿日期:2012-01-10 修回日期:2012-05-09 发布日期:2012-06-07
  • 通讯作者: 徐志广, 刘海洋 E-mail:chzgxu@scnu.edu.cn; chhyliu@scut.edu.cn
  • 基金资助:

    国家自然科学基金(20971046, 21171057)和广东省自然科学基金(10351064101000000)资助项目

Effect of Substituents on Mn―O Bond in Oxo-Manganese(V) Corrole Complexes

HE Jing1, XU Zhi-Guang1, ZENG Yun-Xiu1, XU Xuan1, YU Lan2, WANG Qi2, LIU Hai-Yang2   

  1. 1. Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment, South China Normal University; Guangzhou 510006, P. R. China;
    2. Department of Chemistry, South China University of Technology, Guangzhou 510641, P. R. China
  • Received:2012-01-10 Revised:2012-05-09 Published:2012-06-07
  • Contact: XU Zhi-Guang, LIU Hai-Yang E-mail:chzgxu@scnu.edu.cn; chhyliu@scut.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (20971046, 21171057) and Natural Science Foundation of Guangdong Province, China (10351064101000000).

摘要:

用密度泛函理论(DFT)方法对一系列A3型咔咯锰(V)氧配合物进行了理论计算. 结果表明: 咔咯锰(V)-氧配合物中Mn―O键是由1 个σ键和2 个π键构成的叁键结构; 当咔咯中位取代基由推电子过渡到拉电子性质时, 咔咯骨架紧缩, Mn―O键缩短, 其拉曼光谱的伸缩振动峰往高波数移动; 取代基与氧原子的静电作用模式由正-负吸引转化为负-负排斥, 导致Mn―O键解离能ΔE减少, 即拉电子基团有利于增强咔咯锰(V)-氧配合物氧原子的活泼性.

关键词: 密度泛函理论, 咔咯, 锰-氧配合物, 静电势

Abstract:

Density functional theory (DFT) calculations are used to investigate the effect of substituents on the Mn―O bond in A3-type oxo-manganese(V) corrole complexes. Results indicate that the Mn―O bonds in all the investigated oxo-manganese(V) corrole complexes are triply bonded by one σ and two π bonds. As the electron withdrawing ability of the substituents increases, the corrole skeleton contracts, resulting in a decrease in the Mn―O bond length, and the Mn―O Raman stretching vibration shifts to higher wavenumber. As the electrostatic potential of the substituents changes from positive to negative, the electrostatic interaction between oxygen and substituents changes from a negative-positive electrostatic attraction to a negative-negative electrostatic repulsion. Electron withdrawing substituents enhance oxygen reactivity of corrole Mn-oxo complexes by lowering the Mn―O bond dissociation energy.

Key words: Density functional theory, Corrole, Mn-oxo complex, Electrostatic potential

MSC2000: 

  • O641