Direct Comparison of Subvalent, Polycationic Group 13 Cluster Compounds: Lessons learned on Isoelectronic DMPE Substituted Gallium and Indium Tetracation Salts

The tetracationic, univalent cluster compounds [{M(dmpe)}(4)](4+) (M=Ga, In; dmpe=bis(dimethylphosphino)ethane) were synthesized as their pf salts ([pf](−)=[Al(OR(F))(4)](−); R(F)=C(CF(3))(3)). The four‐membered ring in [{M(dmpe)}(4)](4+) is slightly puckered for M=Ga and almost square planar for M=In. Yet, although structurally similar, only the gallium cluster is prevalent in solution, while the indium cluster forms temperature dependent equilibria that include even the monomeric cation [In(dmpe)](+). This system is the first report of one and the same ligand inducing formation of isoelectronic and isostructural gallium/indium cluster cations. The system allows to study systematically analogies and differences with thermodynamic considerations and bonding analyses, but also to outline perspectives for bond activation using cationic, subvalent group 13 clusters.