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

Abstract

The reaction of palladium powder with the diiodine adduct of Ph₂P(S)NHP(S)Ph₂ (HL) in Et₂O gave the complex Pd(HL)I₂1. 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·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.