Gold(I) Complexes of P,N Ligands and Their Catalytic Activity

Gold(I) complexes were readily prepared by reaction of the respective ligands with (Me2S)AuCl in CH2Cl2. Complexes of formula LAuCl {L = diphenyl(2‐pyridyl)phosphane (PPh2Py), (R)‐(+)‐4‐[(2)‐(diphenylphosphanyl)‐1‐naphthyl]‐N‐[(R)‐1‐phenylethyl]‐1‐phthalazinamine (PINAP)} were obtained when a 1:1 molar ratio of ligand to starting gold precursor was used. When a 2:1 ratio of ligand to gold precursor was used with PPh2Py or MandyPhos as ligands, complexes of the type L2AuCl were obtained. All complexes were fully characterized, and single‐crystal X‐ray structures could be determined for four complexes. Chloride ions were removed by reaction with silver salts, such as AgNTf2, AgOTf and AgBF4, for the use of these complexes as catalysts. After the catalytic reaction with alkynes and alcohols in acetonitrile, a unique trinuclear gold(I) complex derived from [(PPh2Py)Au]BF4 could be characterized by X‐ray structural analysis, showing a mode of catalyst deactivation.