A Trigonal-Prismatic Hexanuclear Technetium(II) Bromide Cluster: Solid-State Synthesis and Crystallographic and Electronic Structure

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• 作者：Erik V. Johnstone ; Daniel J. Grant ; Frederic Poineau ; Laura Fox ; Paul M. Forster ; Longzou Ma ; Laura Gagliardi ; Kenneth R. Czerwinski ; Alfred P. Sattelberger
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：May 20, 2013
• 年：2013
• 卷：52
• 期：10
• 页码：5660-5662
• 全文大小：193K
• 年卷期：v.52,no.10(May 20, 2013)
• ISSN：1520-510X

文摘

The compound Na{[Tc₆Br₁₂]₂Br} has been obtained from the decomposition of TcBr₄ under vacuum in a Pyrex ampule at 450 掳C. The stoichiometry of the compound has been confirmed by energy-dispersive X-ray spectroscopy and its structure determined by single-crystal X-ray diffraction. The compound contains a trigonal-prismatic hexanuclear [Tc₆Br₁₂] cluster. The cluster is composed of two triangular Tc₃Br₆ units linked by multiple Tc鈥揟c bonds. In the Tc₃Br₆ unit, the average Tc鈥揟c distance [2.6845(5) 脜] is characteristic of Tc鈥揟c single bonds, while the average Tc鈥揟c distance between the two triangular units [2.1735(5) 脜] is characteristic of Tc鈮c triple bonds. The electronic structure of the [Tc₆Br₁₂] cluster was studied by first-principles calculations, which confirm the presence of single and triple Tc鈥揟c bonds in the cluster.