a b s t r a c tA series of palladium(II) complexes involving CeH and NeH bond activations of the R 1 rings of thiosemicarbazones {R 1 (R 2 )C 2 eN 3 eN 2 (H)eC 1 (]S)eN 1 HR 3 ; R 1 , R 2 : thiopheneyl, Me, H 2 L 1 (R 3 ¼ Me), H 2 L 2 (R 3 ¼ Ph); R 1 , R 2 : Ph, Me, H 2 L 3 (R 3 ¼ Me), H 2 L 4 (R 3 ¼ Ph); R 1 , R 2 : Ph, Ph, H 2 L 5 (R 3 ¼ Me), H 2 L 6 (R 3 ¼ Ph) and R 1 , R 2 : pyrrole, Me, H 2 L 7 (R 3 ¼ Me), H 2 L 8 (R 3 ¼ Ph)} are described. Methyl group (R 2 ) at C 2 carbon in H 2 L 1 and H 2 L 2 induced CeH bond activation of the thiopheneyl ring and formed cyclometallated complexes, [Pd(k 3 eC 4 ,N 3 ,SeL)(PPh 3 )] (L ¼ L 1 , 1; L 2 , 2). Similarly, phenyl rings (R 1 ) in H 2 L 3 , H 2 L 4 , H 2 L 5 , H 2 L 6 at C 2 carbon have shown CeH activations forming cyclometallated complexes, [Pd(k 3 eC 4 ,N 3 ,SeL)(PPh 3 )] (L ¼ L 3 , 3; L 4 , 4; L 5 , 5; L 6 , 6). However, pyrrole ring did not exhibit similar CeH activation behavior, rather involved NeH activation and formed complexes, [Pd(k 3 eN 4 ,N 3 ,SeL)(PPh 3 )] {L ¼ L 7 , 7; L 8 , 8}. All these complexes have been characterized with the help of analytical data, spectroscopic techniques (IR, 1 H and 31 P NMR), and single crystal X-ray crystallography (1, 2, 4, 5, 7 and 8). The thiosemicarbazone ligands behave as dinegative C 4 , N 3 , S-chelating in 1e6 and N 4 , N 3 , S-chelating in complexes 7 and 8. Interestingly, complexes 2, 4 and 8, with phenyl substituent at N 1 atom, have two independent molecules in their respective crystal lattices.