Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 56, Issue 10, Pages 2582-2587Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201610696
Keywords
alkali metals; concave binding; sandwich products; sumanene; supramolecular assembly
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Funding
- American Chemical Society Petroleum Research Fund
- US National Science Foundation [CHE-1608628]
- Illinois Institute of Technology
- JST, ACT-C, Japan
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1429329] Funding Source: National Science Foundation
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The controlled reaction of Na and Cs, two alkali metals of different ionic sizes and binding abilities, with sumanene (C21H12) affords a novel type of organometallic sandwich [Cs(C21H11-)(2)], which crystallized as a solvent-separated ion pair with a [Na(18-crown-6)(THF)(2)](+) cation (where THF=tetrahydrofuran). The unprecedented double concave encapsulation of a metal ion by two bowl-shaped sumanenyl anions in [Cs(C21H11-)(2)] @ was revealed crystallo-graphically. Evaluation of bonding and energetics of the remarkable product was accomplished computationally (B2PLYP-D/TZVP/ZORA), providing insights into its formation.
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