Gold(0) and gold(III) reactivity towards the tetraphenyldithioimidodiphosphinic acid, [Ph2P(S)NHP(S)Ph2]

The reaction of gold powder with the iodine adduct of Ph2P(S)NHP(S)Ph2 (HL) in Et2O gave the complex [Au(L)I2] under mild reaction conditions. Its crystal structure is comprised of discrete, monomeric molecules with a central AuIII ion bonded to two sulfur atoms by an anionic ligand L and two iodide anions in a slightly distorted square-planar coordination geometry. From the reaction of [AuCl3(tht)] with HL in CH2Cl2 it is possible, besides the main complex [Au(L)]2, to separate the neutral AuI complex [Au(L′2H)], L′ = [Ph2P(S)NP(O)Ph2]−, the crystal structure of which features a AuI ion linearly coordinated to two sulfur atoms and a proton bridging two oxygen atoms of the PO groups. 31P NMR CP MAS spectroscopy is in accordance with the nature of the ligands in the complex. The reaction chemistry of [Au(L′2H)] in CH2Cl2 towards the acid CF3COOH and the organic base 1,8-bis(dimethylamino)naphthalene is reported