Two classes of diastereomerically enriched chiral tridentate ligands incorporating either two oxazolidine and one pyridine (1) or two pyridine and one oxazolidine (2a-c) donor groups have been made in a high-yielding modular fashion from readily available enantiopure amino alcohols and aldehydes. Both ligand classes readily formed metal complexes via 1:1 reactions with trans-PdCl2(PhCN)(2). The compounds Pd(1)Cl-2 and Pd(2a-c)Cl-2 were formed as mixtures of 3 and 2 diastereomers, respectively, owing to indeterminate absolute configuration at the C-2 position of their constituent oxazolidine rings. Within each diastereomeric manifold, the metal complexes existed as equilibrium mixtures of bi- and tridentate isomers in solution, the interconversion between which was very rapid even at -50 degrees C, The fluxional nature of the compounds was inferred from a combination of H-1 and N-15 NMR spectroscopic and solution conductivity data. Substitution of one chloride ligand for hexafluorophosphate gave as mixtures of diastereomers the salts [Pd(1-kappa N,kappa N-2')Cl]PF6 (8) and [Pd(2a-C-kappa N,kappa N',kappa N')Cl]PF6 (12a-c) in which the ligands were coordinated through all three N-donors. A single recrystallization of 8 gave in optically pure form the major diastereomer 8(maj). which was characterized crystallographically. Complexes of 2a-c differed substantially from those of the bis(pyridylmethyl)amine (bpma) ligand family with which they shared direct atom-for-atom connectivity in the coordinating groups, The amines are known to form exclusively the static tridentate complexes [PdCl(bpma-kappa N kappa N-2')]Cl; the difference was attributed to torsional strain associated with the rigid oxazolidine ring in tricoordinated 2a-c.