The Oxidation of Gold Powder by Me3El2 (E P, As) under Ambient Conditions; Structures of [AuI3(PMe3)2], [AuI3(AsMe3)], and [(Me3PO)2H][AuI2]

Unactivated gold powder readily reacts with Me3EI2 (E  P, As) in diethyl ether to form the planar complex [AuI3(AsMe3)] and, surprisingly, the trigonal-bipyramidal complex [AuI3-(PMe3)2] (structure shown on the right); the latter readily hydrolyzes to form [(Me3PO)2H][AuI2]. The oxidation of this noble metal to Au3+ and the production of complexes of different stoichiometries and structures illustrates the oxidizing power and the subtlety of these Me3EI2 reagents.