Systematic assembly of the double molecular boxes: {Cs⊂[CpCo(CN)3]4[Cp*Ru]3} as a tridentate ligand
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Edited by Jack Halpern, University of Chicago, Chicago, IL, and approved January 18, 2002 (received for review December 5, 2001)
Abstract
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 ⊂ Co4Ru3 + M (M = Cp*Rh2+, 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.
Footnotes
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↵ † To whom reprint requests should be addressed. E-mail: rauchfuz{at}uiuc.edu.
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This paper was submitted directly (Track II) to the PNAS office.
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Data deposition: The atomic coordinates have been deposited with the Cambridge Structural Database, Cambridge Crystallographic Data Centre, Cambridge CB2 1EZ, United Kingdom (CSD reference nos. CCDC-174664 and -174665).
- Abbreviations:
- ESI-MS,
- electrospray ionization MS;
- THF,
- tetrahydrofuran;
- Cp,
- cyclopentadienyl;
- Cp*,
- pentamethylcyclopentadienyl;
- PB,
- Prussian blue;
- OTf,
- trifluoromethanesulfonate
- Copyright © 2002, The National Academy of Sciences
