Palladium(II)-coordinated NCR¹ (R¹ = Et ( 1 ), NMe2 (2), Ph (3)) species react smoothly with acyclic nitrones such as the ketonitrones Ph2C=N(O)R⁴ (R⁴ = p-MeC6H4 (4), p-ClC6H4 (5)) and the aldonitrone p- MeC6H4CH=N(O)Me (6) in the corresponding nitrile media. This reaction proceeds as a consecutive two-step intennolecular cycloaddition to give the mono- and bis-2,3-dihydro-1,2,4-oxadiazole complexes [PdCl2(R¹CN){Na= C(R¹)ON(R⁴)Cb(R²R³)}](a-b) (7a-13a; R², R³ = Ph; R⁴ = C6H4Me-p, R¹ = Et (7), NMe2 (8), Ph (9); R⁴ = C6H4Cl-p, R¹ = Et (10), NMe2 (11), Ph (12); R² = H, R³ = C6H4Me-p, R4 = Me, R¹ = NMe2 (13)) and [PdCl2{Na= C(R¹)ON(R⁴)Cb(R²R³)}2](a-b) (7b-13b), respectively. Inspection of the obtained data and their comparison with the previous results indicate that the PdII centers provide substantially greater activation of RCN ligands toward the 1,3-dipolar cycloaddition than the relevant PtII centers. The palladium(II)- mediated 1,3-dipolar cydoaddition of ketonitrones to nitriles is reversible. All complexes were characterized by elemental analyses (C, H, N), high-resolution ESI-MS, and IR and ¹H and 13C{¹H} NMR spectroscopy. The structure of trans- 7b was determined by single-crystal X-ray diffraction. Metal-free 5-NR'2-2,3- dihydro-1,2,4-oxadiazoles (7c--13c) were liberated from the corresponding (2,3-dihydro-1,2,4-oxadiazole)2PdII complexes by treatment with 1,2-(diphenylphosphino)ethane, and the heterocycles were characterized by high-resolution ESI⁺-MS and ¹H and 13C{¹H} spectroscopy. [ABSTRACT FROM AUTHOR]