Immobilization of Volatile and Corrosive Iodine Monochloride (ICI) and I2 Reagents in a Stable Metal-Organic Framework
Immobilization of Volatile and Corrosive Iodine Monochloride (ICI) and I2 Reagents in a Stable Metal-Organic Framework
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DOI：
10.1021/ic500677t
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发表时间：
2014-07-07
影响因子：
4.6
通讯作者：
Xu, Zhengtao
中科院分区：
文献类型：
--
作者：
He, Jun;Duan, Jingjing;Xu, Zhengtao
这里的主要发现是一个强大的和水稳定的金属有机框架（MOP）材料，能够可逆结合ICI和I-2的挥发性和反应性分子。12和ICI的固定化以及由此实现的它们的可控释放促进了这些挥发性物质作为催化剂和试剂在化学和工业过程中的广泛应用。通过在乙腈中加热CuI和有机连接剂TMBP（3，3 ′，5，5 ′-四甲基-4，4 ′-联吡唑），可以方便地以定量产率制备骨架材料TMBP中心点CuI（以下简称TCuI）。TCuI的微孔三维网具有CuI链，其有助于ICI和12分子的有效和可逆结合，以分别产生TCuI中心点ICl和TCuI中心点I-2的化学计量良好定义的加合物。此外，将挥发性化合物如ICI限制在M0 F介质内提供了独特的机会来增强其作为化学试剂的反应性和选择性，如本文所检查的碘化反应所例示的。通过该示例性研究，我们打算激发进一步探索MOF和其他多孔介质（例如，多孔聚合物）用于捕获ICI和其它挥发性试剂（例如，Br-2 SCl 2，S2 Cl 2和SOCl 2）和与多孔介质相关的潜在新反应性。
The major discovery here is a robust and water-stable metal organic framework (MOP) material capable of reversible binding of the volatile and reactive molecules of ICI and I-2. The immobilization of 12 and ICI, as well as their controllable release thus achieved, is to facilitate the wide-ranging applications of these volatile species as catalysts and reagents in chemical and industrial processes. The framework material TMBP center dot CuI (hereafter TCuI) can be conveniently prepared in quantitative yields by heating CuI and the organic linker TMBP (3,3',5,5'-tetramethyl-4,4'-bipyrazol) in acetonitrile. The microporous three-dimensional net of TCuI features CuI chains that contribute to efficient and reversible binding of ICI and 12 molecules, to result in the stoichiometrically well-defined adducts of TCuI center dot ICl and TCuI center dot I-2, respectively. Moreover, the confinement of a volatile compound like ICI within the MOF medium provides unique opportunities to enhance its reactivity and selectivity as a chemical reagent, as is exemplified by the iodination reactions examined herein. With this exemplary study, we intend to stimulate interest in further exploring MOFs and other porous media (e.g., porous polymers) for entrapping ICI and other volatile reagents (e.g., Br-2 SCl2, S2Cl2, and SOCl2) and for potentially novel reactivity associated with the porous medium.