Silver-Free Activation of Ligated Gold(I) Chlorides: The Use of [Me3NB12Cl11]− as a Weakly Coordinating Anion in Homogeneous Gold Catalysis

Phosphane and N‐heterocyclic carbene ligated gold(I) chlorides can be effectively activated by Na[Me3NB12Cl11] (1) under silver‐free conditions. This activation method with a weakly coordinating closo‐dodecaborate anion was shown to be suitable for a large variety of reactions known to be catalyzed by homogeneous gold species, ranging from carbocyclizations to heterocyclizations. Additionally, the capability of 1 in a previously unknown conversion of 5‐silyloxy‐1,6‐allenynes was demonstrated. Gold without silver: Ligated gold(I) chlorides can be effectively activated under silver‐free conditions by Na[Me3NB12Cl11]. This activation method with a weakly coordinating anion was shown to be suitable for various reactions known to be catalyzed by homogeneous gold species, ranging from carbo‐ to heterocyclizations (see figure).