Step‐by‐Step Synthesis of the Endohedral Stannaspherene [Ir@Sn12]3− via the Capped Cluster Anion [Sn9Ir(cod)]3− |
| |
Authors: | Jian‐Qiang Wang Dr. Saskia Stegmaier Bernhard Wahl Dr. Thomas F. Fässler Prof. Dr. |
| |
Affiliation: | Department Chemie, Technische Universit?t München, Lichtenbergstra?e 4, 85747 Garching/München (Germany), Fax: (+49)?89‐289‐13186 |
| |
Abstract: | The endohedral stannaspherene cluster anion [Ir@Sn12]3? was synthesized in two steps. The reaction of K4Sn9 with [IrCl(cod)]2 (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 [Sn9Ir(cod)]3?. 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@Sn12]3? was obtained and characterized as the [K(2,2,2‐crypt)]+ salt. The isolation of [Sn9Ir(cod)]3? as an intermediate product establishes that the formation of the stannaspherene [Ir@Sn12]3? occurs through the oxidation of [Sn9Ir(cod)]3?. Among the structurally characterized tetrel cluster anions, [Ir@Sn12]3? 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 Ih point symmetry. |
| |
Keywords: | cluster compounds intermetalloids polyhedrons synthesis design Zintl anions |
|
|