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DFT Study of Iron Tetraphenylporphyrin Chloride and Iron Pentafluorophenylporphyrin Chloride
Qing-zhang Lv*,Yan Lu,Jian-ji Wang
Author NameAffiliationE-mail
Qing-zhang Lv* College of Chemistry and Environmental Sciences, Henan Normal University, Xinxiang 453007, China lvqz@henannu.edu.cn 
Yan Lu College of Chemistry and Environmental Sciences, Henan Normal University, Xinxiang 453007, China  
Jian-ji Wang College of Chemistry and Environmental Sciences, Henan Normal University, Xinxiang 453007, China  
Abstract:
The geometry optimizations and the single point energy calculations of iron tetraphenylporphyrin chloride Fe(TPP)Cl and iron tetraphenylporphyrin chloride (Fe(TPP)Cl), iron pentafluorophenylporphyrin chloride (Fe(TPPF20)Cl) were carried out by using the Density Functional Theory (DFT) UB3LYP with STO-3G* and 6-31G* basis sets, respectively. The electronic properties and the structures of high-lying molecular orbitals were analyzed in detail. The results show that partial spin is transferred from the Fe atom to the porphyrin ring and some electron with the spin opposite to the unpaired electron on the Fe atom is transferred from the porphyrin ring to the Fe atom. The π- and σ-type bonding between the Fe atom and the porphyin ring cause the transfer. The fluorination enhances the electron transfer and the chemical stability of the complex. The high stability is important for the complex possessing high catalytic activity. The catalysis mechanism of oxygen molecule activation on the complex surface is also discussed based on the symmetry of the molecular orbitals.
Key words:  Iron porphyrin, DFT, Molecular orbital, Activation mechanism of molecular oxygen
FundProject:
氯化四苯基铁卟啉和氯化四全氟代苯基铁卟啉的密度泛函研究
吕庆章*,,卢雁,王键吉
摘要:
用密度泛函B3LYP/STO-3G*和B3LYP/6-31G*方法对血红素模拟物分子铁卟啉分子Fe(TPP)Cl和Fe(TPPF20)Cl进行了几何结构优化和单点能量计算,对它们的分子轨道、电荷密度和自旋密度分布做了详细分析.数据表明,有部分自旋电子由Fe原子向卟啉环转移,同时有部分自旋与Fe原子3d轨道上单电子自旋相反的电子由卟啉环向Fe原子迁移.两个铁卟啉分子的最高占有轨道结构相似,电子和自旋在卟啉环与Fe原子之间的转移是由于Fe-卟啉环间的?键和?键相互作用引起的,氯化四全氟代苯基铁卟啉分子中的这种
关键词:  铁卟啉, 密度泛函, 分子轨道, 活化分子氧机理
DOI:10.1360/cjcp2006.19(3).227.6
分类号: