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

Aydogan, Akin;Bangle, Rachel E.;De Kreijger, Simon;Dickenson, John C.;Troian-Gautier, Ludovic;et.al.
(2021) Catalysis Science & Technology — Vol. 11, n° 24, p. 8037-8051 (2021)

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Abstract
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.
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Aydogan, A., Bangle, R. E., De Kreijger, S., Dickenson, J. C., Singleton, M., Cauët, E., Cadranel, A., Meyer, G. J., Elias, B., Sampaio, R. N., & Troian-Gautier, L. (2021). Mechanistic investigation of a visible light mediated dehalogenation/cyclisation reaction using iron(iii), iridium(iii) and ruthenium(ii) photosensitizers. Catalysis Science & Technology, 11(24), 8037-8051. https://doi.org/10.1039/d1cy01771c (Original work published 2021)