Products Cited in Publications Worldwide Complete ligand substitution and oxidation of the metal center in the photochemical reaction of CpM (CO) 2 I (M= Fe, Ru) with chelating β-diketones

Complete ligand substitution and oxidation of the metal center in the photochemical reaction of CpM (CO) 2 I (M= Fe, Ru) with chelating β-diketones

Jarzyński, Szymon; Doroszko, Cyprian; Jamroz, Daria; Stefanowska-Kątna, Kinga; Walkowiak, Jędrzej; Wojtulewski, Sławomir; Zakrzewski, Janusz; Rudolf, Bogna

DOI: PMID:

Abstract

The visible-light irradiation of solutions of CpFe(CO)2I (Cp = (η5-C5H5)), acetylacetone (or other β-diketones), and diisopropylamine in toluene led to the substitution of all ligands with β-diketonate anions and the oxidation of FeII to FeIII. The only product was Fe(β-diketonate)3, which exclusively formed even when using an equimolar ratio of CpFe(CO)2I and diketone. The reaction occurred under both anaerobic and aerobic conditions. The proposed reaction mechanism assigns the key role to the noninnocent behavior of the β-diketonate ligands. Dioxygen or the acetylacetone acts as oxidant. The ruthenium complex CpRu(CO)2I reacts with acetylacetone in a similar way to the corresponding iron complex, but irradiation with UV light is required to assure an acceptable yield of the product. All obtained complexes were analyzed by NMR, FT-IR, and ESI-MS, and one was subjected to single-crystal and powder X-ray diffraction analysis, which revealed its mer stereochemistry.

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Fe(dibm)3

A116707524444-72-298%

Fe(dibm)3

92.0/1g

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Iron(III) acetylacetonate

A17151114024-18-197%

Iron(III) acetylacetonate

66.0/500g

Detail
Fe(TMHD)3

A75547414876-47-298%

Fe(TMHD)3

70.0/5g

Detail