Fixation of Zinc(II) Ion to Dioxygen in a Highly Deformed Porphyrin: Implications for the Oxygen Carrier Mechanism of Distorted Heme

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• 作者：Zaichun Zhou ; Xiaochun Zhou ; Qiuhua Liu ; Xi Zhang ; Haomin Liu
• 刊名：Organic Letters
• 出版年：2015
• 出版时间：August 21, 2015
• 年：2015
• 卷：17
• 期：16
• 页码：4078-4081
• 全文大小：304K
• ISSN：1523-7052

文摘

Three saddle-type nonplanar zinc porphyrins strapped by two short alkyl linkers have been synthesized. The deformation induced by the linkers can cause a spectral red shift of >30 nm compared with the absorption maxima of regular porphyrins and can also regulate the electronic structure of the central zinc(II) ion. The zinc(II) ion then complexes and activates a free dioxygen to form a superoxide group ligand by enlarging the splitting of energy levels of d orbitals under strong core deformation. The fixation of dioxygen can be reasonably explained by the Dewar鈥揅hatt鈥揇uncanson model. These results indicate that this type of saddle porphyrin has the potential to be used as a new model system of heme.