Department Chemie, Technische Universität München, Lichtenbergstrasse 4, 85747 Garching/München, Germany.
Chemistry. 2010 Feb 8;16(6):1793-8. doi: 10.1002/chem.200902815.
The endohedral stannaspherene cluster anion Ir@Sn(12) was synthesized in two steps. The reaction of K(4)Sn(9) with IrCl(cod) (cod: 1,5-cyclooctadienyl) in ethylenediamine (en) solution first yielded the K(2,2,2-crypt) salt (2,2,2-crypt: 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) of the capped cluster anion Sn(9)Ir(cod). Subsequently, crystals of this compound were dissolved in en, followed by the addition of triphenylphosphine or 1,2-bis(diphenylphosphino)ethane and treatment at elevated temperatures. Ir@Sn(12) was obtained and characterized as the K(2,2,2-crypt) salt. The isolation of Sn(9)Ir(cod) as an intermediate product establishes that the formation of the stannaspherene Ir@Sn(12) occurs through the oxidation of Sn(9)Ir(cod). Among the structurally characterized tetrel cluster anions, Ir@Sn(12) is a unique example of a stannaspherene, and one of the rare spherical clusters encapsulating a metal atom that is not a member of Group 10. Single-crystal structure determination shows that the novel Zintl ion cluster has nearly perfect icosahedral I(h) point symmetry.
笼型锡原子簇阴离子Ir@Sn(12)通过两步法合成。K(4)Sn(9)与IrCl(cod)(cod：1,5-环辛二烯)在乙二胺(en)溶液中的反应首先得到了K(2,2,2-穴醚)盐(2,2,2-穴醚：4,7,13,16,21,24-六氧杂-1,10-二氮杂环辛烷)的 capped 原子簇阴离子Sn(9)Ir(cod)。随后，将该化合物的晶体溶解在 en 中，然后加入三苯基膦或 1,2-双(二苯基膦基)乙烷，并在高温下处理。得到了Ir@Sn(12)，并作为K(2,2,2-穴醚)盐进行了表征。作为中间产物的Sn(9)Ir(cod)的分离确立了锡原子笼Ir@Sn(12)的形成是通过Sn(9)Ir(cod)的氧化实现的。在结构表征的四乙撑簇阴离子中，Ir@Sn(12)是锡原子笼的一个独特例子，也是少数几个封装非第十族金属原子的球形簇之一。单晶结构测定表明，这种新型 Zintl 离子簇具有近乎完美的二十面体 I(h)点对称。
