Oxidation of palladium powder by the adduct Ph2P(S)NHP(S)Ph2.I2. Crystal structure of PdL2

The reaction of palladium powder with the diiodine adduct of Ph2P(S)NHP(S)Ph2 (HL) in Et2O gave the complex Pd(HL)I2 1. Subsequent crystallisation from CH3CN separates the complex PdL2. Its crystal structure comprises discrete, monomeric molecules where a PdII is in a square planar geometry coordinated to four sulfur atoms of two bidentate anionic ligands. The electrochemistry of HL·I2 and PdL2 has been studied by cyclic voltammetry. FT-IR and 31P NMR spectroscopies are in accordance with the nature of the ligand in the two complexes. Hybrid-DFT calculations have been performed on a model complex Pd[H2P(S)NP(S)H2]2 to gain insight on the electronic nature of PdL2.