The synthesis of new organotin compounds of the general formula L 2SnR2 (L = N-(3-tert-butylsalicylidene)-2,3,4,5,6- pentafluoroaniline; R = CH3 (1), n-C4H9 (3)) and L′2SnR2 (L′ = Ar-(3-tert- butylsalicylidene)aniline; R = CH3 (2), n-C4H9 (4)) is described herein. The compounds were characterized by 1H, 13C, and 119Sn NMR in solution; in some cases a fluxional behavior was observed by variable-temperature experiments. Characterization by single-crystal X-ray diffraction analysis has been obtained for compounds 1, 2, and 4. The reactivity of the synthesized compounds toward ionizing agents was studied by an NMR-tube reaction. Compounds 2 and 4 underwent an alkyl abstraction reaction with the carbenium salt [C(C6H5) 3]+[B(C6F5)4]". The obtained cationic species exhibited some activity in the oligomerization of ethylene under mild conditions, producing short-chain oligomers, with saturated end groups and methyl branches.