Spectroscopic, electrochemical and X-ray crystallographic properties of a novel palladium(II) complex of thioamide deprotonated di-2-pyridyl ketone thiosemicarbazone (dpktsc-H)−

AbstractThe reaction between di-2-pyridyl ketone thiosemicarbazone (dpktsc) and PdCl2(CH3CN)2, generated in situ from the reaction between PdCl2 and CH3CN, gave the unprecedented [Pd2Cl3(κ5-Npy,Nim,S,Npy,Nam-dpktsc-H)]·2CH3CN (1) complex (py = pyridine, im = imine and am = amide). The identity of 1 was confirmed via its elemental analysis and spectroscopic properties. Infrared and 1H-NMR spectra confirmed the coordination of (dpktsc-H)− to the palladium ions. The electronic absorption spectra measured in dmso and dmf and density functional theory (DFT) calculations revealed metal-to-ligand charge-transfer (MLCT), d–d and intra-ligand charge-transfer (ILCT) electronic transitions. X-ray structural analysis on a crystal of [Pd2Cl3(κ5-Npy,Nim,S,Npy,Nam-dpktsc-H)]·H2O (2) grown from dmf solution of 1 confirmed its formulation and showed the solid-state structure contains a web of molecules locked via a network of non-covalent interactions. Electrochemical measurements on 1 in dmf revealed metal- and ligand-ba...