Institute of Structural Chemistry, Chemical Research Center, Hungarian Academy of Sciences, H-1025 Budapest, Pusztaszeri ut 59-67, Hungary.
J Am Chem Soc. 2009 Mar 4;131(8):2815-7. doi: 10.1021/ja809067t.
We synthesized and structurally characterized the first cyanoaurate-based organotin polymer Me(3)Sn[Au(CN)(2)] (1), which exhibits unusual ion-exchange properties. In the structure of 1, the void space of the 2D grids formed via Au...Au bonding is filled by arrays of zigzag chains joined by weak Au...Au interactions. Interestingly, the practically insoluble polymer 1 shows unusual ion-exchange properties. The polymer Me(2)SnAu(CN)(2) (2) was obtained in the metathesis reaction of 1 with Me(2)SnCl(2). Compound 2 displays cyanide-bridged uninodal four-connected 3D nets with 6(5).8 topology corresponding to the CdSO(4) prototype. Interestingly, 2 can be converted back into 1 by metathesis with Me(3)SnCl. Moreover, we performed a series of metal-exchange experiments in which 1 was soaked in aqueous solutions of bivalent transition-metal cations M(2+) (M = Co, Ni, Cu, Zn). As a result, 1 was completely converted into transition-metal cyanoaurates. To our knowledge, this represents the first study revealing the metal-exchange properties of a cyanoaurate-based heterometallic polymer.
我们合成并结构表征了首例氰基金属有机锡聚合物 Me(3)Sn[Au(CN)(2)] (1)，其展现出了不同寻常的离子交换性质。在 1 的结构中，通过 Au...Au 键形成的二维网格的空隙空间被由弱的 Au...Au 相互作用连接的锯齿形链阵列填充。有趣的是，实际上不溶的聚合物 1 表现出了不同寻常的离子交换性质。通过 1 与 Me(2)SnCl(2)的复分解反应得到了聚合物 Me(2)SnAu(CN)(2) (2)。化合物 2 显示出具有氰桥的单节点四连接的 3D 网络，具有对应于 CdSO(4)原型的 6(5).8 拓扑结构。有趣的是，2 可以通过与 Me(3)SnCl 的复分解反应重新转化为 1。此外，我们进行了一系列的金属交换实验，其中 1 被浸泡在二价过渡金属阳离子 M(2+)（M = Co、Ni、Cu、Zn）的水溶液中。结果，1 完全转化为过渡金属氰基金属配合物。据我们所知，这代表了首例揭示氰基金属有机锡杂金属聚合物的金属交换性质的研究。
