Reactivity of Liquid Ammonia Solutions of the Zintl Phase K12Sn17 towards Mesitylcopper(I) and Phosphinegold(I) Chloride
Reactivity of Liquid Ammonia Solutions of the Zintl Phase K12Sn17 towards Mesitylcopper(I) and Phosphinegold(I) Chloride
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DOI：
10.1002/chem.201404594
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发表时间：
2014-12-08
影响因子：
4.3
通讯作者：
Faessler, Thomas F.
中科院分区：
文献类型：
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作者：
Benda, Christian B.;Waibel, Markus;Faessler, Thomas F.
为了更深入地了解类金属间簇合物的反应性，研究了含有[Sn-4]（4-）和[Sn-9]（4-）簇合物阴离子的Zintl相K12 Sn 17的反应性。K 12 Sn 17与氯化膦金（I）反应得到K-7[（eta（2）-Sn-4）Au（eta（2）-Sn-4）]（NH 3）（16）（1）和K-17[（eta（2）-Sn-4）Au（eta（2）-Sn-4）]（2）（NH 2）（3）（NH 3）（52）（2），它们都含有阴离子[（Sn-4）Au（Sn-4）]（7-）（1a），该阴离子由通过中心金原子连接的两个[Sn-4]（4-）四面体组成。阴离子1a表示第一二元Au- Sn聚阴离子。从该反应中，还得到溶剂合物结构[K（[2.2.2]crypt）]（3）K[Sn-9]（NH3）（18）（3; [2.2.2]crypt= 4，7，13，16，21，24-六氧杂-1，10-二氮杂双环[8.8.8]二十六烷）。在液氨中，在[18]冠-6存在下，在均三甲苯基铜与K_（12）Sn_（17）的类似反应中，（[18]冠-6）]（[18]冠-6）（MesH）（NH3）][Cu@Sn-9]（thf）（4（[18] crown-6= 1，4，7，10，13，16-hexaoxacyclocycline，MesH=mesitylene，thf=tetrahydrofuran），并以[Cu@Sn-9]（3-）簇合物为特征。用[2.2.2] crypt作为螯合剂的类似反应导致形成[K[2.2.2]crypt][MesCuMes]（5）的晶体。4中均三甲苯的共结晶和5中[MesCuMes]（-）（5a）的存在提供了强有力的证据，表明裸Cu原子迁移到Sn-9阴离子是通过从均三甲苯铜释放Mes（-）阴离子而发生的，Mes（-）阴离子迁移到另一个均三甲苯铜以形成5a或随后质子化以产生MesH。
To gain more insight into the reactivity of intermetalloid clusters, the reactivity of the Zintl phase K12Sn17, which contains [Sn-4](4-) and [Sn-9](4-) cluster anions, was investigated. The reaction of K12Sn17 with gold(I) phosphine chloride yielded K-7[(eta(2)-Sn-4) Au(eta(2)-Sn-4)](NH3)(16) (1) and K-17[(eta(2)-Sn-4) Au(eta(2)-Sn-4)](2)(NH2)(3)(NH3)(52) (2), which both contain the anion [(Sn-4) Au(Sn-4)](7-) (1a) that consists of two [Sn-4](4-) tetrahedra linked through a central gold atom. Anion 1a represents the first binary Au- Sn polyanion. From this reaction, the solvate structure [K([2.2.2]crypt)](3)K[Sn-9](NH3)(18) (3; [2.2.2]crypt=4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) was also obtained. In the analogous reaction of mesitylcopper with K12Sn17 in the presence of [18] crown-6 in liquid ammonia, crystals of the composition [K([18]crown-6)](2)[K([18]crown-6)(MesH)(NH3)][Cu@Sn-9](thf) (4) were isolated ([18] crown-6=1,4,7,10,13,16-hexaoxacyclooctadiene, MesH=mesitylene, thf=tetrahydrofuran) and featured a [Cu@Sn-9](3-) cluster. A similar reaction with [2.2.2] crypt as a sequestering agent led to the formation of crystals of [K[2.2.2]crypt][MesCuMes] (5). The cocrystallization of mesitylene in 4 and the presence of [MesCuMes](-) (5a) in 5 provides strong evidence that the migration of a bare Cu atom into an Sn-9 anion takes place through the release of a Mes(-) anion from mesitylcopper, which either migrates to another mesitylcopper to form 5a or is subsequently protonated to give MesH.