Hybrid Cluster-Cages Formed via Cyanometalate Condensation: Cs<b>⊂</b>Co₄Ru₆S₂(CN)₁₂, Co₄Ru₉S₆(CN)₉, and Rh₄Ru₉S₆(CN)₉ Frameworks

Condensation of cyanometalates and cluster building blocks leads to the formation of hybrid molecular cyanometalate cages. Specifically, the reaction of {Cs⊂[CpCo(CN)3]4[Cp*Ru]3} and [(cymene)2Ru3S2(NCMe)3]PF6 produced {Cs⊂[CpCo(CN)3]4[(cymene)2Ru3S2][Cp*Ru]3}(PF6)2, Cs⊂Co4Ru6S22+. Single-crystal X-ray diffraction, NMR spectroscopy, and ESI-MS measurements show that Cs⊂Co4Ru6S22+ consists of a Ru4Co4(CN)12 box fused with a Ru3S2 cluster via a common Ru atom. The reaction of PPN[CpCo(CN)3] and 0.75 equiv of [(cymene)2(MeCN)3Ru3S2](PF6)2 in MeCN solution produced {[CpCo(CN)3]4[(cymene)2Ru3S2]3}(PF6)2, Co4Ru9S62+. Crystallographic analysis, together with NMR and ESI-MS measurements, shows that Co4Ru9S62+ consists of a Ru3Co4(CN)9 “defect box” core, wherein each Ru is fused to a Ru3S2 clusters. The analogous condensation using [Cp*Rh(CN)3]- in place of [CpCo(CN)3]- produced the related cluster-cage Rh4Ru9S62+. Electrochemical analyses of both Co4Ru9S62+ and Rh4Ru9S62+ can be rationalized in the context of reduction at the cluster and the CoIII subunits, the latter being affected by the presence of alkali metal cations.