The 5-aryl-3-(2′-pyridiyl)-1,2,4-triazine ligands under study L 1 ; 5-(3-methoxyphenyl)-(PyTZ3Me-OPh) L 2 ; 5-(4-methoxyphenyl)-(PyTZ4MeOPh) L 3 ; 5-(4-trifluoromethylphenyl)-(PyTZ4CF 3 Ph) L 4 ; 5-(4-fluorophenyl)-(PyTZ4FPh) L 5 ; and tris-3,5,6-(2′-pyridyl)-1,2,4-triazine (Py 3 TZ) L 6 ] react with [(COD)PdCl 2 ] (COD = 1,5-cyclooctadiene) to form complexes [(L 1-6 )PdCl 2 ] with N,N bidentate binding ligands, also including the potentially N,N,N tridentate ligand L 6 . This was concluded from an in-depth NMR spectroscopic study of the new complexes and from comparison with Pd-terpy complexes [(R′ terpy)PdCl]Cl [R′terpy = 4′-R′-2,2′:6′,2′′-terpyridine; R′ = H or SMe], showing definite tridentate N,N,N coordination, and with the Pd-bpy complexes [(bpy)Pd(Mes)Cl] and [(bpy)PdCl 2 ], show-Eur.