Two structurally isomeric substituted N,N-dimethylethanamines have been prepared. Treatment of the 2,4-di-tert-butylphenyl isomer with PdII ions generated the ortho-metalated complexes. On the other hand, treatment of the 2,5-di-tert-butylphenyl-substituted amine resulted in the unexpected chemoselective cleavage of one of the three N–C bonds, thus generating the corresponding secondary amine. The N-demethylation process could be catalyzed at room temperature by palladium(II) catalysts such as PdCl2 or Pd(OAc)2. Furthermore, treatment with a stoichiometric amount of PdII ions gave a metal complex in which both secondary amines were bound to Pd in an N-monodentate fashion. When triethylamine was introduced, one of the N-ethyl groups in NEt3 was cleaved, and an unexpected heteroamine complex was produced. The products generated were isolated and characterized by X-ray crystallography. Mechanistic insights into the cyclometalation and C–N cleavage observed are discussed.