Hybrid Cluster-Cages Formed via Cyanometalate Condensation: Cs⊂Co 4Ru6S2(CN)12, CO4Ru 9S6(CN)9, and Rh4Ru 9S6(CN)9 Frameworks

Matthew L. Kuhlman, Thomas Rauchfuss

Research output: Contribution to journalArticlepeer-review

Abstract

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]PF 6 produced {Cs⊂-[CpCo(CN)3]4[(cymene) 2Ru3S2][Cp*Ru]3}(PF 6)2, Cs⊂Co4Ru6S2 2+. Single-crystal X-ray diffraction, NMR spectroscopy, and ESI-MS measurements show that Cs⊂Co4Ru6S2 2+ consists of a Ru4Co4(CN)12 RU4CO4(CN)12 box fused with a Ru3S2 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 Rh 4Ru9S62+, Electrochemical analyses of both Co4Ru9S62+ and Rh 4Ru9S62+ 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.

Original languageEnglish (US)
Pages (from-to)430-435
Number of pages6
JournalInorganic Chemistry
Volume43
Issue number2
DOIs
StatePublished - Jan 26 2004

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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