Spectroscopic, electrochemical and X-ray crystallographic properties of a novel palladium(II) complex of thioamide deprotonated di-2-pyridyl ketone thiosemicarbazone (dpktsc-H)−
The 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-based redox processes. In contrast to the electrochemical decomposition of uncoordinated dpktsc, coordinated (dpktsc-H)− in 1 does not undergo electrochemical decomposition. Electrochemical titrations of 1 with p-toluenesulfonic acid monohydrate (p-TSOH) revealed electro-catalytic proton reduction. Over-potential (η) of 180 mV for the H2 evolution was observed and is comparable to several molecular electro-catalysts for proton reduction. Controlled-potential electrolysis confirmed the electro-catalytic proton reduction by the Pd-complex. Electrochemical reactions of CO2 in the presence of 1 exhibited a proton dependence, and metal- and ligand-based electrochemical reaction.
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