Department of Chemistry, University at Albany, State University of New York, 1400 Washington Avenue, Albany, NY, 12222, USA.
Department of Chemistry, Illinois Institute of Technology, Chicago, IL, 60616, USA.
Angew Chem Int Ed Engl. 2017 Mar 1;56(10):2582-2587. doi: 10.1002/anie.201610696. Epub 2017 Feb 7.
The controlled reaction of Na and Cs, two alkali metals of different ionic sizes and binding abilities, with sumanene (C H ) affords a novel type of organometallic sandwich [Cs(C H ) ] , which crystallized as a solvent-separated ion pair with a [Na(18-crown-6)(THF) ] cation (where THF=tetrahydrofuran). The unprecedented double concave encapsulation of a metal ion by two bowl-shaped sumanenyl anions in [Cs(C H ) ] was revealed crystallographically. Evaluation of bonding and energetics of the remarkable product was accomplished computationally (B2PLYP-D/TZVP/ZORA), providing insights into its formation.
钠和铯与 sumanene（C H ）的受控反应生成了一种新型的有机金属夹心 [Cs(C H ) ] ，它结晶为具有 [Na(18-冠-6)(THF) ] 阳离子（其中 THF=四氢呋喃）的溶剂分离离子对。在 [Cs(C H ) ] 中，金属离子被两个碗状的 sumanenyl 阴离子前所未有的双重凹面封装在晶体中。通过计算（B2PLYP-D/TZVP/ZORA）对显著产物的键合和能量进行了评估，为其形成提供了深入了解。
