Relationship between structure and catalytic activity of chloro-iron tetraphenylporphyrin compounds
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Relationship between structure and catalytic activity of chloro-iron tetraphenylporphyrin compounds
CIESC JournalIssue 6, Pages: 1339-1345(2006)
作者机构:
1. 北京工业大学环能学院化学化工系,绿色化学与精细化工研究所,北京,100022
2. 北京工业大学生命科学与生物工程学院,北京,100022
3. 华南理工大学化工与能源学院,广东,广州,510640
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基金信息:
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Online First:25 June 2006,
Published:25 June 2006
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WANG Lanzhi, SHE Yuanbin, ZHONG Rugang, et al. Relationship between structure and catalytic activity of chloro-iron tetraphenylporphyrin compounds[J]. CIESC Journal, 2006, (6): 1339-1345.
DOI:
WANG Lanzhi, SHE Yuanbin, ZHONG Rugang, et al. Relationship between structure and catalytic activity of chloro-iron tetraphenylporphyrin compounds[J]. CIESC Journal, 2006, (6): 1339-1345.DOI:
Relationship between structure and catalytic activity of chloro-iron tetraphenylporphyrin compounds
Nine chloro-iron tetraphenylporphyrin (RTPPFeCl) compounds were designed and synthesized
and their catalytic activities were characterized by using dioxygen liquid-phase oxidation of p-nitrotoluene (PNT) to p-nitrobenzoic acid (PNBA) as model reaction
and their molecular frontier orbital energies EHOMO
ELUMO
ΔEL-H etc were calculated by using the PM3 semi-empirical molecular orbital method.The QSAR(quantitative relationship between structure and catalytic activity)of chloro-iron tetraphenylporphyrin (RTPPFeCl) was investigated by combining activity (yield of PNBA) with EHOMO and ΔEL-H of 9 catalysts.It was found that there was excellent linear correlation between catalytic activity and frontier orbital energy.Through linear regression the following equations were obtained: that is
for T(o-R)PPFeCl
Y=71.766-8.166EHOMO-10.701ΔEL-H
and correlation coefficient R=0.964.For T(p-R)PPFeCl: Y=80.031-9.297EHOMO-14.288ΔEL-H
and correlation coefficient R=0.998.It was also concluded that the effect of EHOMO on catalytic activity was larger than that of ΔEL-H for 5-coordinate of iron porphyrins.EHOMO was the main structure parameter influencing catalytic activities of 5-coordinate of iron-porphyrin compounds.Moreover the catalytic activities of two iron-porphyrin compounds with substituted methyl group were predicted according to this relationship.The results showed that the catalytic activity of metalloporphyrin was consistent with that predicted.The results made it possible to use the model of structure-activity relationship to predict unknown catalysts.Finally
the same correlation between the catalytic activities and electronic structure parameters of the Co
Mn and Fe metal porphyrins were obtained according to the authors’ research work published in three papers.These results will help not only to enrich biomimetic catalytic theory
but also to design excellent biomimetic catalysts from molecular levels.