All-Hydrocarbon-Ligated Superatomic Gold/Aluminum Clusters

Key strategies in cluster synthesis include the use of modulating agents (e.g., coordinating additives). We studied the influence of various phosphines exhibiting different steric and electronic properties on the reduction of the Au-(I) precursor to Au(0) clusters. We report a synthesis of the bimetallic clusters [Au6(AlCp*)(6)] = [Au(6)Al6]-(Cp*)(6) (1) and [HAu7(AlCp*)(6)] = [HAu7Al6]-(Cp*)(6) (2) (Cp* = pentamethylcyclopentadiene) using Au-(I) precursors and AlCp*. The cluster [Au2(AlCp*)5] = [Au2Al5]-(Cp*)(5) (3) was isolated and identified as an intermediate species in the reactions to 1 and 2. The processes of cluster growth and degradation were investigated by in situ 1H NMR and LIFDI-MS techniques. The structures of 1 and 2 were established by DFT geometry optimization. These octahedral clusters can both be described as closed-shell 18-electron superatoms.