Aryl-Cl vs heteroatom-Si bond cleavage on the route to the photochemical generation of σ,π-heterodiradicals.

The photochemistry of aryl chlorides having a X-SiMe group (X = O, NR, S, SiMe) 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.Graphical abstract.