Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu₃SnH yields tributyltin halide as a byproduct.

The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions, where Bu₃SnH undergoes homolytic cleavage in the presence of light to form a tributyltin radical. This radical abstracts the halogen from an alkyl halide, forming an alkyl radical intermediate and tributyltin halide. The radical intermediate further abstracts hydrogen from tributyltin hydride and produces an alkane and a tributyltin radical, which propagates the reaction.

As C–Br and C–I bonds are weaker than C–Cl bonds, daylight is sufficient to initiate the hydrogenolysis of alkyl bromides and iodides. In contrast, alkyl fluorides are unreactive because of the strong C–F bonds. The hydrogenolysis of alkyl chlorides using Bu₃SnH requires a high concentration of tributyltin radicals, which is achieved by adding an initiator to the reaction mixture. AIBN is the most widely used initiator, as it undergoes thermal homolysis above 60 °C to form nitrile-stabilized radicals. These radicals abstract hydrogen from tributyltin hydride, forming the tributyltin radical, which propagates the reaction.

Peroxides are not used as initiators because peroxide radicals are highly reactive and can abstract hydrogen from organic halides leading to unwanted side reactions.