Systematic assembly of the double molecular boxes: {Cs⊂[CpCo(CN)3]4[CpRu]3} as a tridentate ligand

• Published in: Proceedings of the National Academy of Sciences - PNAS Vol. 99; no. 8; pp. 4889 - 4893
• Main Authors: Contakes, Stephen M, Kuhlman, Matthew L, Ramesh, Maya, Wilson, Scott R, Rauchfuss, Thomas B
• Format: Journal Article
• Language: English
• Published: United States National Acad Sciences 16-04-2002; National Academy of Sciences
• Series: From the Cover
• Subjects: Bridged-Ring Compounds - chemistry; Cations; Cesium - chemistry; Chemistry; Cobalt - chemistry; Crystallography, X-Ray; Cyclopentanes - chemistry; Ligands; Macromolecular Substances; Models, Chemical; Organometallic Compounds - chemistry; Physical Sciences; Ruthenium - chemistry
• ISSN: 0027-8424; 1091-6490
• DOI: 10.1073/pnas.062647799

Cubic cage compounds composed of Co-CN-Ru linkages have been prepared which illustrate the following features: ( i ) new motifs for alkali metal ion complexation (i.e., cationic receptors for cations), ( ii ) a new family of triaza-metalloligands, and ( iii ) a double box-like cage. The cages are synthesized by the condensation of [CpCo(CN) 3 ] − and [Cp*Ru(NCMe) 3 ] + (cyclopentadienyl, Cp; pentamethylcyclopentadienyl, Cp*) the presence of Cs + . The species {Cs⊂{[CpCo(CN) 3 ] 4 [Cp*Ru] 4 } + and {Cs⊂{[CpCo(CN) 3 ] 4 [Cp*Ru] 3 [Cp*Rh]} 2+ illustrate the box-completion reaction Cs ⊂ Co 4 Ru 3 + M (M = Cp*Rh 2+ , Cp*Ru + ). With the naked ion precursors [Na(NCMe) 6 ] + and [Fe(NCMe) 6 ] 2+ , the box-completion reactions afforded {Na{Cs⊂[CpCo(CN) 3 ] 4 [Cp*Ru] 3 ]} 2 } + and {Fe{Cs⊂ [CpCo(CN) 3 ] 4 [Cp*Ru] 3 ]} 2 } 2+ . These cages provide the first examples, to our knowledge, of the double-box motif.