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)Ph-2 (HL) in Et2O gave the complex Pd(HL)I-2 1. Subsequent crystallisation from CH3CN separates the complex PdL2. Its crystal structure comprises discrete, monomeric molecules where a Pd-II is in a square planar geometry coordinated to four sulfur atoms of two bidentate anionic ligands. The electrochemistry of HL .I-2 and PdL2 has been studied by cyclic voltammetry. FT-IR and P-31 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)H-2](2) to gain insight on the electronic nature of PdL2.