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Production of a putative iron(V)-oxocorrole species by photo-disproportionation of a bis-corrole-diiron(IV)-mu-oxo dimer: implication for a green oxidation catalyst.

ABSTRACT: Photodisproportionation of a bis-corrole-diiron(IV)-mu-oxo dimer gave a corrole-iron(III) species and a corrole-iron(V)-oxo species that can be detected and studied in real time. Air oxidation of the corrole-iron(III) species regenerated the bis-corrole-diiron(IV)-mu-oxo dimer, allowing the development of a photocatalytic method for organic oxidations using molecular oxygen and visible light.

SUBMITTER: Harischandra DN

PROVIDER: S-EPMC2720094 | biostudies-other | 2009 May

REPOSITORIES: biostudies-other

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Production of a putative iron(V)-oxocorrole species by photo-disproportionation of a bis-corrole-diiron(IV)-mu-oxo dimer: implication for a green oxidation catalyst.

Harischandra Dilusha N DN Lowery Gerald G Zhang Rui R Newcomb Martin M

Organic letters 20090501 10

Photodisproportionation of a bis-corrole-diiron(IV)-mu-oxo dimer gave a corrole-iron(III) species and a corrole-iron(V)-oxo species that can be detected and studied in real time. Air oxidation of the corrole-iron(III) species regenerated the bis-corrole-diiron(IV)-mu-oxo dimer, allowing the development of a photocatalytic method for organic oxidations using molecular oxygen and visible light. ...[more]

PMID: 19361171

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Project description:Iron(iv)-oxo species have been identified as the active intermediates in key enzymatic processes, and their catalytic properties are strongly affected by the equatorial and axial ligands bound to the metal, but details of these effects are still unresolved. In our aim to create better and more efficient oxidants of H-atom abstraction reactions, we have investigated a unique heteroleptic diiron phthalocyanine complex. We propose a novel intramolecular approach to determine the structural features that govern the catalytic activity of iron(iv)-oxo sites. Heteroleptic ?-nitrido diiron phthalocyanine complexes having an unsubstituted phthalocyanine (Pc1) and a phthalocyanine ligand substituted with electron-withdrawing alkylsulfonyl groups (PcSO2R) were prepared and characterized. A reaction with terminal oxidants gives two isomeric iron(iv)-oxo and iron(iii)-hydroperoxo species with abundances dependent on the equatorial ligand. Cryospray ionization mass spectrometry (CSI-MS) characterized both hydroperoxo and diiron oxo species in the presence of H2O2. When m-CPBA was used as the oxidant, the formation of diiron oxo species (PcSO2R)FeNFe(Pc1)[double bond, length as m-dash]O was also evidenced. Sufficient amounts of these transient species were trapped in the quadrupole region of the mass-spectrometer and underwent a CID-MS/MS fragmentation. Analyses of fragmentation patterns indicated a preferential formation of hydroperoxo and oxo moieties at more electron-rich iron sites of both heteroleptic ?-nitrido complexes. DFT calculations show that both isomers are close in energy. However, the analysis of the iron(iii)-hydroperoxo bond strength reveals major differences for the (Pc1)FeN(PcSO2R)FeIIIOOH system as compared to (PcSO2R)FeN(Pc1)FeIIIOOH system, and, hence binding of a terminal oxidant will be preferentially on more electron-rich sides. Subsequent kinetics studies showed that these oxidants are able to even oxidize methane to formic acid efficiently.

Dataset Information

Production of a putative iron(V)-oxocorrole species by photo-disproportionation of a bis-corrole-diiron(IV)-mu-oxo dimer: implication for a green oxidation catalyst.

Publications

Production of a putative iron(V)-oxocorrole species by photo-disproportionation of a bis-corrole-diiron(IV)-mu-oxo dimer: implication for a green oxidation catalyst.

Similar Datasets

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