Hybrid cluster-cages formed via cyanometalate condensation:: CS⊂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 {Cssubset of[CpCo(CN)(3)](4)[Cp*Ru](3)} and [(cymene)(2)Ru3S2(NCMe)(3)]PF6 produced {Cssubset of[CpCo(CN)(3)](4)[(cymene)(2)Ru3S2][Cp*Ru](3)}(PF6)(2), Cs subset of Co4Ru6S22+. Single-crystal X-ray diffraction, NMR spectroscopy, and ESI-MS measurements show that Cs subset of 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)(3)Ru3S2](PF6)(2) in MeCN solution produced {[CpCo(CN)(3)](4)[(cymene)(2)Ru3S2](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 Co-III subunits, the latter being affected by the presence of alkali metal cations.