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Mechanistic investigation of a visible light mediated dehalogenation/cyclisation reaction using iron(iii), iridium(iii) and ruthenium(ii) photosensitizers

par Aydogan, Akin;Bangle, Rachel;De Kreijger, Simon;Dickenson, John J.C.;Singleton, Michael M.L.;Cauet, Emilie ;Cadranel, Alejandro;Meyer, Gerald John;Elias, Benjamin ;Sampaio, Renato R.N.;Troian Gautier, Ludovic
Référence Catalysis science & technology, 11, 24, page (8037-8051)
Publication Publié, 2021-12

Article révisé par les pairs

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Résumé :

The mechanism of a visible light-driven dehalogenation/cyclization reaction was investigated using ruthenium(ii), iridium(iii) and iron(iii) photosensitizers by means of steady-state photoluminescence, time-resolved infrared spectroscopy, and nanosecond/femtosecond transient absorption spectroscopy. The nature of the photosensitizer was found to influence the product distribution such that the dehalogenated, non-cyclized products were only detected for the iron photosensitizer. Strikingly, with the iron photosensitizer, large catalytic yields required a low dielectric solvent such as dichloromethane, consistent with a previous publication. This low dielectric solvent allowed ultrafast charge-separation to outcompete geminate charge recombination and improved cage escape efficiency. Further, the identification of reaction mechanisms unique to the iron, ruthenium, and iridium photosensitizer represents progress towards the long-sought goal of utilizing earth-abundant, first-row transition metals for emerging energy and environmental applications.