Si<sub>4sub><sup>4-sup> in Solution - First Solvate Crystal Structure of the Ligand-free Tetrasilicide Tetraanion in Rb<sub>1.2sub>K<sub>2.8sub>Si<sub>4sub>·7NH<sub>3sub>

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• 作者：Corinna Lorenz ; Stefanie G&auml ; rtner and Nikolaus Korber
• 刊名：Zeitschrift für anorganische und allgemeine Chemie
• 出版年：2017
• 出版时间：January 2017
• 年：2017
• 卷：643
• 期：2
• 页码：141-145
• 全文大小：350K
• ISSN：1521-3749

文摘

We report the first solvate structure of the silicide anion Si<sub>4sub><sup>4&ndash;sup>, which provides circumstantial evidence of the stability of the highly charged anion in liquid ammonia solutions. The solvate Rb<sub>1.2sub>K<sub>2.8sub>Si<sub>4sub>·7NH<sub>3sub> crystallized from a mixture of the ternary compound K<sub>6sub>Rb<sub>6sub>Si<sub>17sub> with the transition metal complex [(C<sub>6sub>H<sub>5sub>)<sub>3sub>P]<sub>2sub>Ni(CO)<sub>2sub> [bis(triphenylphosphine)dicarbonylnickel] in the presence of the chelating agents 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane) and [2.2.2]cryptand (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) in liquid ammonia. Single X-ray diffraction analysis confirms the presence of the Si<sub>4sub><sup>4&ndash;sup> anion in the crystal structure of Rb<sub>1.2sub>K<sub>2.8sub>Si<sub>4sub>·7NH<sub>3sub>, which represents the first solvate compound of the naked tetrasilicide tetraanion. All five crystallographically independent cation positions show mixed occupancy by Rb<sup>+sup> and K<sup>+sup>.