Adamantylisonitrile and benzonitrile were reacted with bulky substituted organotin trihydride [Ar*SnH 3 ] [Ar* = (C 6 H 3 -2,6-Trip 2 ), Trip = 2,4,6-triisopropylphenyl]. They do not show any reaction at room temperature as well as at 80 °C. After activation of the organotin trihydride with diethylmethylamine in the isonitrile case three hydrogen atoms were transferred from the tin atom to the isonitrile unit and a carbon tin bond was formed to give an intramolecular adduct between a diorganostannylene and a dialkylamine. Benzonitrile as well as adamantylisonitrile react both with low-valent organotin hydride [Ar*SnH] 2 . Benzonitrile shows an insertion reaction with the low-valent organotin hydride to yield a dimeric insertion product, whereas the isonitrile carbon atom of adamantylisonitrile abstracts three hydrogen atoms from the low-valent organotin hydride to give an equimolar mixture between (adamantylmethylamido)organostannylene and a bis(isonitrile)distannyne adduct.