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Oxidation of iron(III) tetramesitylporphyrin with dimethyldioxirane.

Autorzy

Stanisław Wołowiec

Lechosław Latos-Grażyński

Rok wydania

1998

Czasopismo

Inorganic Chemistry

Numer woluminu

37

Strony

2984-2988

DOI

10.1021/ic9715963

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

The oxidation of (TMP)FeIIIClO4 in solution with dimethyldioxirane-d6 has been examined by 1H NMR spectroscopy. The reaction of (TMP)FeIIIClO4 with dimethyldioxirane-d6 in a solvent mixture of dichloromethane-d2/methanol-d4 (4:1 v/v) produced two intermediates:  (TMP)FeIV(CD3O)2 and X(TMP•)FeIVO, which could be directly observed at low temperatures. When the (TMP)FeIIIClO4−dimethyldioxirane-d6 reaction was carried out in dichloromethane-d2, the loss of iron(III) tetramesitylporphyrin resonances was accompanied by growth of resonances due to (TMP)FeIV(CD3O)2 and X(TMP•)FeIVO. A set of ferryl porphyrin cation radicals X(TMP•)FeIVO (X − ligands available) was identified. The formation of a variety of ligands resulted from side reaction pathways which include dioxirane and dichloromethane-d2. Addition of dimethyldioxirane-d6 to the acetone-d6 solution of (TMP)FeIIIClO4 gave mainly iron(III) porphyrin cation radical [(TMP•)FeIII((CD3)2CO)2]+ and a small amount of ferryl porphyrin cation radicals [(CD3)2CO(TMP•)FeIVO]+. Typically, in the (TMP)FeIIIClO4−dioxirane systems the formation of one-electron oxidation product (iron(IV) porphyrin or iron(III) porphyrin radical) predominates, rendering such an approach less effective in generation of green ferryl porphyrin cation radicals than use of iodozobenzene, peroxyacids, or ozone.

Słowa kluczowe

Cations, Chemical reactions, Ligands, Oxidation, Pyrroles

Adres publiczny

https://doi.org/10.1021/ic9715963

Strona internetowa wydawcy

https://www.acs.org/content/acs/en.html

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