Metathesis reactions of the N-thienylidene-L/D-methionine methyl ester ligand (th-metMe) with suitable palladium starting complexes afforded coordination complexes of the type PdX(2)(th-metMe), PdX(Me)(th-metMe), and [Pd(Me)(th-metMe)(L ")](O3SCF3) (X = Cl, Br, I; and L " = MeCN, pyridine, picoline, lutidine) which were studied by NMR with respect to the fluxional behavior of the diastereomeric PdNS six-membered ring chelates. The structure of PdCl2(th-metMe) in the solid state (a = 13.318(5) Angstrom, b = 11.365(2) Angstrom, c = 13.579(5) Angstrom, beta = 96.66(4)degrees) showed a square planar coordination complex in which the ligand is chelating via the imine nitrogen (Pd-N = 2.030(7) Angstrom) and the methionine sulfur donor atom (Pd-S-1 = 2.283(2) Angstrom). The square planar geometry is completed by the chlorides (Pd-Cl-1 = 2.275(3) Angstrom (trans to the imine nitrogen) and Pd-Cl-2 2.322(2) Angstrom (trans to the sulfur donor)). The dimeric [PdCl(L’)](2) complex (L’ = anionic alpha-methoxycarbonyl, alpha-(2-thienylmethylidene)amine, alpha "-(methylthio)ethane) was formed by C-H activation of the chiral carbon atom of the alpha-amino acid moiety.