Complete ligand substitution and oxidation of the metal center in the photochemical reaction of CpM(CO)<sub>2</sub>I (M = Fe, Ru) with chelating β-diketones
The visible-light irradiation of solutions of CpFe(CO)<sub>2</sub>I (Cp = (η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)), acetylacetone (or other β-diketones), and diisopropylamine in toluene led to the substitution of all ligands with β-diketonate anions and the oxidation of Fe<sup>II</sup> to Fe<sup>III</sup>. The only product was Fe(β-diketonate)<sub>3</sub>, which exclusively formed even when using an equimolar ratio of CpFe(CO)<sub>2</sub>I and diketone. The reaction occurred under both anaerobic and aerobic conditions. The proposed reaction mechanism assigns the key role to the non-innocent behavior of the β-diketonate ligands. Dioxygen or the acetylacetone acts as oxidant. The ruthenium complex CpRu(CO)<sub>2</sub>I 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 <i>mer</i> stereochemistry.
Authors
- Jędrzej Walkowiak
- Sławomir Wojtulewski (ORCID: https://orcid.org/0000-0001-5535-4525)
- Szymon Jarzyński (ORCID: https://orcid.org/0000-0002-1558-098X)
- Bogna Rudolf (ORCID: https://orcid.org/0000-0003-0319-0535)
- Janusz Zakrzewski (ORCID: https://orcid.org/0000-0002-3403-1126)
- Daria Jamroz
- Kinga Stefanowska-Kątna
- Cyprian Doroszko
Institutions
- University of Białystok (PL)
- University of Łódź (PL)
- Adam Mickiewicz University in Poznań (PL)
Publication Details
- Journal
- Dalton Transactions
- Published
- 2025-01-01
- DOI
- https://doi.org/10.1039/d5dt00294j
- Primary Topic
- Organometallic Complex Synthesis and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Uniwersytet Łódzki
- European Regional Development Fund