Gold Teflates Revisited: From the Lewis Superacid [Au(OTeF5)3] to the Anion [Au(OTeF5)4]−

Abstract

AbstractA new synthetic access to the Lewis acid [Au(OTeF5)3] and the preparation of the related, unprecedented anion [Au(OTeF5)4]−with inorganic or organic cations starting from commercially available and easy‐to‐handle gold chlorides are presented. In this first extensive study of the Lewis acidity of a transition‐metal teflate complex by using different experimental and quantum chemical methods, [Au(OTeF5)3] was classified as a Lewis superacid. The solid‐state structure of the triphenylphosphine oxide adduct [Au(OPPh3)(OTeF5)3] was determined, representing the first structural characterization of an adduct of this highly reactive [Au(OTeF5)3]. Therein, the coordination environment around the gold center slightly deviates from the typical square planar geometry. The [Au(OTeF5)4]−anion shows a similar coordination motif.