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Published on: May 21, 2019
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Copper(II) Carbaporphyrins: Oxygenation Reactivities Dependent upon Coordinating Structures
Fangling Deng1, Xinrun Ge1, Zhongyu Deng1
1Key Laboratory of Chemical Biology and Traditional Chinese Medicine, Ministry of Educational of China, and Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, China.
Inorganic Chemistry
|January 31, 2024
Summary
Copper(II) metalations of carbaporphyrins yield distorted complexes. Increased coordination distortion enhances reactivity, enabling O-atom insertion and conversion to methoxy- and hydroxyporphyrins.
Area of Science:
- Coordination Chemistry
- Organometallic Chemistry
- Porphyrin Chemistry
Background:
- Carbaporphyrins are porphyrin analogs with a pyrrolic carbon replaced by a methylene group.
- Copper(II) complexes of porphyrins and related macrocycles are widely studied for their catalytic and electronic properties.
- The coordination geometry around the metal center significantly influences the reactivity of metalloporphyrins.
Purpose of the Study:
- To investigate the copper(II) metalation of carbaporphyrins and characterize the resulting complexes.
- To explore the reactivity of these copper(II) carbaporphyrin complexes under various conditions.
- To synthesize novel functionalized carbaporphyrin derivatives.
Main Methods:
- Synthesis of copper(II) carbaporphyrin complexes (1-Cu to 4-Cu) via metalation.
- Chemical transformations of copper(II) carbaporphyrins using copper(II) acetate in different solvents and with additives.
- Characterization of products including O-atom insertion, methoxylation, hydroxylation, and diketoporphyrinogen formation.
Main Results:
- Copper(II) metalation of carbaporphyrins 1-4 yielded complexes 1-Cu to 4-Cu with varying degrees of Cu(II) square-planar coordination distortion.
- Complexes 2-Cu and 3-Cu underwent O-atom insertion upon treatment with Cu(OAc)2, forming 2-OCu and 3-OCu.
- Complexes 3-Cu and 4-Cu were converted to meso-methoxynickel(II) porphyrins (3-OMe, 4-OMe) in methanol, and 4-Cu yielded a 5,15-diketoporphyrinogen (4-O) in the presence of acetic acid. meso-Hydroxynickel(II) porphyrin 3-OH was obtained from 3-OCu.
Conclusions:
- The reactivity of Cu(II) carbaporphyrin complexes is enhanced by increased distortion in the Cu(II) square-planar coordination.
- These findings demonstrate a versatile synthetic route to functionalized carbaporphyrin derivatives.
- The study highlights the potential of carbaporphyrins as platforms for developing novel metallo-organic compounds.
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