Suppression of Realgar Cage Degradation during Complexation: Formation of Hybrid Coordination Polymers with As4S4, PAs3S3, and Cu(I) Halide Building Blocks

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• 作者：Patrick Schwarz ; Joachim Wachter ; Manfred Zabel
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：December 19, 2011
• 年：2011
• 卷：50
• 期：24
• 页码：12692-12696
• 全文大小：370K
• 年卷期：v.50,no.24(December 19, 2011)
• ISSN：1520-510X

文摘

Realgar, As₄S₄, reacts with Cr(CO)₅THF under cage degradation to give As₄S₃路Cr(CO)₅ (1). The reverse structural change is found if solutions of 1 in CH₂Cl₂ react with equimolar amounts of PAs₃S₃路W(CO)₅ and CuX (X = Cl, Br, I) in CH₃CN under biphasic diffusion conditions. The resulting coordination polymers 2鈥?b>4 contain a reconstituted realgar molecule along with the PAs₃S₃ cage. The crystal structures of (CuX)(As₄S₄)(PAs₃S₃) (X = Cl: 2; Br: 3) are characterized by one-dimensional (1D) (CuX)(As₄S₄) strands, which are formed by alternating As₄S₄ cages and CuX dumbbells. Terminal PAs₃S₃ molecules are coordinated to copper by apical phosphorus and bridging realgar through sulfur. The As₃ triangles of the resulting (CuX)(As₄S₄)(PAs₃S₃) strands interact with halides of neighbored strands to give a folded three-dimensional (3D) network. The structure of (CuI)₃(As₄S₄)(PAs₃S₃) (4) contains 1D (Cu₃I₃)_n strands as backbones, which are bridged by sulfur atoms of two 畏^1:2-As₄S₄ molecules while PAs₃S₃ confines the resulting sheet. The As₃ triangles at the surface of the layers interact with iodide of the next layer to form a layered 3D network.