The 2-(2-pyridyl)benzothiazolines of general formula {C6H4N(H)CS}(C5H4N)R (R = H, 1; R = Me, 2; R = Ph, 3 and, R = C5H4N-2, 4) in presence of Pd(tmeda)Me2 or Pd(μ-Cl)(η3-C3H5)2 are precursors of N,N,S-tridentate Schiff bases for the formation of organopalladium(II) complexes. From the opening reactions of the thiazoline ring, the mononuclear methylpalladium(II) chlorocomplexes (1a–4a), the dinuclear (η3–allyl)palladium(II) dichloro complexes (1b–3b) and, the trinuclear (η3–allyl)palladium(II) trichloro complex 4c were obtained. Crystals structures of complexes 1a·1/6THF and 3b are stabilized by π---π stacking, CH---π, H---S and CH---Cl. The formation of η3-allylcomplexes 1b–3b and 4c by DFT calculations was also evaluated. Display omitted The synthesis of mononuclear Pd(II) complexes of type Pd(Ln)Me (n = 1–4, 1a–4a) and dinuclear (η3–allyl)palladium(II) dichloro complexes Pd2(Ln)(η3-C3H5)Cl2 (n = 1–3, 1b–3b) derived from 2-R-(2-pyridyl)benzothiazolines used as Schiff bases precursors (R = H, 1; R = Me, 2; R = Ph, 3; R = C5H4N-2, 4) is reported. The formation of the trinuclear complex Pd3(L4)(η3-C3H5)2Cl3 (4c) and its behavior in solution is also described. Complexes 1a–4a, 1b–3b and 4c were obtained from the thiazole ring-opening reaction of precursors 1–4 in presence of the Pd(tmeda)Me2 and Pd(μ -Cl)(η3-C3H5)2 starting materials. The {Ln}− anionic Schiff bases obtained showed a versatile behavior towards coordination to Pd(II) ion; in 1a–4a the ligand acted as tricoordinate whilst in 1b–3b and 4c, {Ln}− acted as mono- and tridentate ligand, respectively. 1a–4a were stable complexes in DMSO‑d6 solution; the dinuclear 1b–3b and trinuclear 4c complexes showed the dissociation of S→Pd bond in DMSO‑d6 solution. Complexes 3a and 3b were characterized by X-ray diffraction studies and a distorted square planar geometry around the central Pd(II) ion was observed in the two five–membered chelate rings. A systematic analysis based on DFT calculation of the structural, electronic, and thermochemistry properties was performed for η3-ally complexes 1b–3b and 4c.