Table Along these considerations, the next transformation we had in mind was the C-H functionalisation of unactivated aliphatic hydrocarbons in Giese-type coupling reaction. The coupling of cyclohexane with acrylonitrile was studied as initial model reaction (Table ). The simplest catalyst enabling this reaction is a homoleptic bismuth polychloride anion releasing a chlorine radical for HAT. Indeed, a combination of BiCl 3 and TBACl (1:2) (entry 1) gave the desired coupling product 2c in 72% yield, while heterogenous materials Bi 2 O 3 and BiOCl lead to unproductive degradation of the alkene (entries 2 and 3). To close the catalytic cycle of this redox-neutral reaction, a reduction step is necessary which is facilitated by the reduced bismuth (II) catalyst fragment but not by the heterogenous materials. Control experiments without BiCl 3 and in the absence of light confirmed essential role of both in this transformation (entries 4 and 5).