Theoretical Study on Electronic Structural Properties of Catalytically Reactive Metalloporphyrin Intermediates

Catalysts

Ruping Liu¹  Yonggang Yang¹  Luhai Li¹  Yumeng Han¹  Aijing Gao¹  Lixin Mo¹  Meijuan Cao¹  Yaling Li¹  Zhicheng Sun¹  Furui He²  Yuanyuan Liu²  Yang Zhou² 

[1] Beijing Engineering Research Center of Printed Electronics, Beijing Institute of Graphic Communication, Beijing 102600, China;School of Chemical Engineering, Technology, Hainan University, Haikou, Hainan 570228, China;

关键词: density functional theory;    porphyrin intermediates;    ground state;    mulliken charge;    frontier molecular orbital (fmo);   

DOI  :  10.3390/catal10020224

来源: DOAJ

【 摘 要 】

Metalloporphyrins have attracted great attention in the potential application of biomimetic catalysis. Especially, they were widely investigated as green catalysts in the chemical oxidation of various hydrocarbons through the catalytic activation of molecular oxygen. The structural properties of active central metal ions were reported to play a decisive role in catalytic activity. However, those delicate structural changes are difficult to be experimentally captured or elucidated in detail. Herein, we explored the electronic structural properties of metalloporphyrins (metal porphyrin (PM^II, PM^IIICl)) and their corresponding catalytically active intermediates (metal(III)-peroxo(PM^III-O₂), metal(III)-hydroperoxo(PM^III-OH), and metal(IV)-oxo(PM^IV=O), (M=Fe, Mn, and Co)) through the density functional theory method. The ground states of these intermediates were determined based on the assessment of relative energy and the corresponding geometric structures of ground states also further confirmed the stability of energy. Furthermore, our analyses of Mulliken charges and frontier molecular orbitals revealed the potential catalytic behavior of reactive metalloporphyrin intermediates.

【 授权许可】

Unknown