Stack by Stack: From the Free Cyclopentadienylgermanium Cation Via Heterobimetallic Main‐Group Sandwiches to Main‐Group Sandwich Coordination Polymers

Heterobimetallic cationic sandwich complexes [M(μ‐Cp)M′Cp](+) of group 13 (M=Ga, In) and group 14 (M′=Ge, Sn) elements have been prepared as [WCA](−) salts (WCA=Al(OR(F))(4); OR(F)=OC(CF(3))(3)). Their molecular structures include free apical gallium or indium atoms. The sandwich complexes were formed in the reactions of [M(HMB)](+)[WCA](−) (HMB=C(6)Me(6)) with the free metallocenes [M′Cp(2)]. Their structures are related to known stannocene and stannocenium salts; the unprecedented germanium analogues, namely the free germanocenium cation [GeCp](+) and the corresponding triple‐decker complex cation [CpGe(μ‐Cp)GeCp](+), are described herein. By variation of the reaction conditions, these sandwich complexes can be transformed into the group 13/14 mixed cationic coordination polymer [{In(HMB)(μ‐SnCp(2))}(n)][WCA](n). This polymeric chain motif was also successfully replicated by the synthesis of complexes [{Ga/In(HMB)(μ‐FeCp(2))}(n)][WCA](n) containing FeCp(2) as a bridging ligand.