Gold(0) and Gold( III ) Reactivity towards the Tetraphenyldithioimidodiphosphinic Acid, [Ph 2 P(S)NHP(S)Ph 2 ]

The reaction of gold powder with the iodine adduct of Ph 2 P(S)NHP(S)Ph 2 (H L ) in Et 2 O gave the complex [Au( L )I 2 ] under mild reaction conditions. Its crystal structure is comprised of discrete, monomeric molecules with a central Au III 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 [AuCl 3 (tht)] with H L in CH 2 Cl 2 it is possible, besides the main complex [Au( L )] 2 , to separate the neutral Au I complex [Au( L′ 2 H)], L′ = [Ph 2 P(S)NP(O)Ph 2 ] − , the crystal structure of which features a Au I ion linearly coordinated to two sulfur atoms and a proton bridging two oxygen atoms of the PO groups. 31 P NMR CP MAS spectroscopy is in accordance with the nature of the ligands in the complex. The reaction chemistry of [Au( L′ 2 H)] in CH 2 Cl 2 towards the acid CF 3 COOH and the organic base 1,8‐bis(dimethylamino)naphthalene is reported. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)