Abstract
The photochemistry of aryl chlorides having a X-SiMe3 group (X = O, NR, S, SiMe2) tethered to the aromatic ring has been investigated in detail, with the aim to generate valuable ϭ,π-heterodiradicals. Two competitive pathways arising from the excited triplet state of the aromatics have been observed, namely heterolysis of the aryl–chlorine bond and homolysis of the X–silicon bond. The former path is found in chlorinated phenols and anilines, whereas the latter is exclusive in the case of silylated thiophenols and aryl silanes. A combined experimental/computational approach was pursued to explain such a photochemical behavior.
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L. D. T., F. R. S.P. and M.F. thanks the Universitiamo crowfunding project (University of Pavia) for partial support.
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Dedicated to Prof. Angelo Albini in the occasion of his 75th birthday.
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Di Terlizzi, L., Roncari, F., Crespi, S. et al. Aryl–Cl vs heteroatom–Si bond cleavage on the route to the photochemical generation of σ,π-heterodiradicals. Photochem Photobiol Sci 21, 667–685 (2022). https://doi.org/10.1007/s43630-021-00119-6
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DOI: https://doi.org/10.1007/s43630-021-00119-6