Cyanometalate cages with exchangeable terminal ligands

Julie L. Boyer, Haijun Yao, Matthew L. Kuhlman, Thomas B. Rauchfuss, Scott Wilson

Research output: Contribution to journalArticlepeer-review


The coordination chemistry of the unusual metallo-ligand Cs⊂[CpCo(CN)3]4[Cp*Ru]3 (Cs⊂Co4Ru3) is described with attention to the behavior of the ligand itself, its binding to Lewis-acidic metal cations, and its ability to stabilize catalytically relevant Ru-PPh3 fragments. A series of tests demonstrate that the "rim" [CpCo(CN)3] - groups in Cs⊂Co4Ru3 are exchangeable. Upon treatment with [(MeC5H4)Co(CN)3] - (Co′) Cs⊂Co4Ru3 undergoes vertex exchange to give Cs⊂Co4-xCo′xRu3. Similarly the cage is degraded by CO. Most convincing, Cs⊂Co 4Ru3 reacts with PhNH3OTf to precipitate the polymer PhNH3CpCo(CN)3 and form the molecular box [Cs⊂Co4Ru4]+. Treatment of Cs⊂Co 4Ru3 with [M(NCMe)x]PF6 (M = Cu, Ag) gave the Lewis acidic cages {Cs⊂[CpCo(CN)3] 4[Cp*Ru]3M(NCMe)}PF6, which reacted with tertiary phosphane ligands to give adducts [Cs⊂Co4Ru 3M(PPh3)]PF6. Lewis acidic octahedral vertices were installed using Fe, Ni, and Ru reagents. The boxes [Cs⊂Co 4Ru3M(NCMe)3]2+ (M = Ni, Fe) formed readily from the reaction Cs⊂Co4Ru3 with [Ni(NCMe)6](BF4)2 and [Fe(NCMe) 6]-(PF6)2. Displacement of the MeCN ligands gives [Cs⊂Co4Ru3Ni(9-ane-S3)](BF4) 2. A series of boxes were prepared by the reaction of Cs⊂Co 4Ru3 and RuCl2(PPh3)3, RuHCl(PPh3)3, and [(C6H6)Ru(NCMe) 3](PF6)2. The derivative of the hydride, [Cs⊂Co4Ru3Ru(NCMe)(PPh3) 2](PF6)2, was characterized crystallographically.

Original languageEnglish (US)
Pages (from-to)2721-2728
Number of pages8
JournalEuropean Journal of Inorganic Chemistry
Issue number18
StatePublished - 2007


  • Cage compounds
  • Cyanide
  • Heterometallic complexes
  • Hydrogen bonds
  • Ruthenium

ASJC Scopus subject areas

  • Inorganic Chemistry


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