Acta Phys. -Chim. Sin. ›› 2012, Vol. 28 ›› Issue (07): 1658-1664.doi: 10.3866/PKU.WHXB201205101

• THEORETICAL AND COMPUTATIONAL CHEMISTRY • Previous Articles     Next Articles

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).

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