[2 + 3] Cycloaddition of N-methyl-C-phenylnitrone to transition metal coordinated (E)-cinnamonitrile occurs exclusively at the nitrile CN bond, leading to Δ⁴-1,2,4-oxadiazoline complexes, from which the heterocyclic ligand can be released and isolated in high yield. In contrast, the reaction of the nitrone with free cinnamonitrile involves the CC bond only, yielding a diastereomeric mixture of isoxazolidine-4-carbonitriles. Microwave irradiation enhances the reaction rates of both transformations considerably, without changing their regioselectivity with respect to the thermal reactions. The two nitrile ligands in complexes of the type [MCl₂(cinnamonitrile)₂] (M = Pt or Pd) are significantly different in reactivity. Thus, short-time microwave irradiation allows for the selective synthesis of the mono-cycloaddition product [PtCl₂(cinnamonitrile)(oxadiazoline)], even in the presence of an excess of nitrone. Using longer irratiation times, this complex can be further transformed into the bis-cycloaddition product [PtCl₂(oxadiazoline)₂]. The latter compound is also produced when thermal heating is applied, however, the formation of the mono-cycloaddition product fails to be selective under thermal conditions.