Double Concave Cesium Encapsulation by Two Charged Sumanenyl Bowls

Sarah N Spisak; Zheng Wei; Andrey Yu Rogachev; Toru Amaya; Toshikazu Hirao; Marina A Petrukhina

doi:10.1002/anie.201610696

Double Concave Cesium Encapsulation by Two Charged Sumanenyl Bowls

Angew Chem Int Ed Engl. 2017 Mar 1;56(10):2582-2587. doi: 10.1002/anie.201610696. Epub 2017 Feb 7.

Authors

Sarah N Spisak¹, Zheng Wei¹, Andrey Yu Rogachev², Toru Amaya³, Toshikazu Hirao^{3

4}, Marina A Petrukhina¹

Affiliations

¹ Department of Chemistry, University at Albany, State University of New York, 1400 Washington Avenue, Albany, NY, 12222, USA.
² Department of Chemistry, Illinois Institute of Technology, Chicago, IL, 60616, USA.
³ Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Yamada-oka, Suita, Osaka, 565-0871, Japan.
⁴ The Institute of Scientific and Industrial Research, Osaka University, Mihoga-oka, Ibaraki, Osaka, 567-0047, Japan.

PMID: 28170146
DOI: 10.1002/anie.201610696

Abstract

The controlled reaction of Na and Cs, two alkali metals of different ionic sizes and binding abilities, with sumanene (C₂₁ H₁₂ ) affords a novel type of organometallic sandwich [Cs(C₂₁ H₁₁^- )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(C₂₁ H₁₁^- )₂ ]^- was revealed crystallographically. Evaluation of bonding and energetics of the remarkable product was accomplished computationally (B2PLYP-D/TZVP/ZORA), providing insights into its formation.

Keywords: alkali metals; concave binding; sandwich products; sumanene; supramolecular assembly.

Publication types

Research Support, Non-U.S. Gov't